Catalysts and methods for polymer synthesis

ABSTRACT

The present invention provides unimolecular metal complexes having increased activity in the copolymerization of carbon dioxide and epoxides. Also provided are methods of using such metal complexes in the synthesis of polymers. According to one aspect, the present invention provides metal complexes comprising an activating species with co-catalytic activity tethered to a multidentate ligand that is coordinated to the active metal center of the complex.

PRIORITY CLAIM

This application is a continuation of U.S. patent application Ser. No.15/251,668 (now U.S. Pat. No. 9,951,096), filed Aug. 30, 2016, which isa continuation of U.S. patent application Ser. No. 14/615,902, filedFeb. 6, 2015 (now U.S. Pat. No. 9,505,878), which is a continuation ofU.S. patent application Ser. No. 13/755,112, filed Jan. 31, 2013 (nowU.S. Pat. No. 8,951,930), which is a divisional application of U.S.patent application Ser. No. 13/059,967, filed on Feb. 18, 2011 (now U.S.Pat. No. 8,633,123), which is a national phase application under 35U.S.C. § 371 of PCT International Application No. PCT/US2009/054773,filed Aug. 24, 2009, which claims priority to U.S. Provisional PatentApplication Ser. No. 61/091,013, filed Aug. 22, 2008; U.S. ProvisionalPatent Application Ser. No. 61/096,313, filed Sep. 11, 2008 and U.S.Provisional Patent Application Ser. No. 61/098,739, filed Sep. 19, 2008.The entire contents of each of these priority applications areincorporated herein by reference.

BACKGROUND

Catalysts capable of effecting the copolymerization of epoxides andcarbon dioxide to form aliphatic polycarbonates (APCs) have been knownin the art since the 1960s. The early catalysts were based onheterogeneous zinc compounds and suffered from low reactivity, a lack ofselectivity for polymer formation vs. cyclic carbonate formation, and atendency to produce polycarbonates contaminated with ether linkages.

Improved catalysts based on transition metals have been discovered overthe past decade or so. These newer catalysts have increased reactivityand improved selectivity. Nevertheless, even using highly activecatalysts such as those disclosed in U.S. Pat. No. 7,304,172, thereaction times required to make high molecular weight polymer aretypically quite long. In addition, the best-performing catalystsdisclosed in the '172 patent require the addition of a separateco-catalyst to achieve optimum activity.

Attempts to address these shortcomings have been made. Catalystsdescribed by Nozaki and co-workers (Angew. Chem. Int. Ed. 2006, 45,7274-7277) tether an amine co-catalyst to a ligand of the catalyst.These next-generation catalytic systems suffer from lengthy andcomplicated syntheses and undesirable induction times prior to onset ofpolymerization. There remains a need for catalysts that have increasedactivity that will further reduce the polymerization time required toproduce high molecular weight APCs.

SUMMARY

The present invention provides, among other things, unimolecularcatalyst systems having activity in the copolymerization of carbondioxide and epoxides and methods of using the same. In some embodiments,the present invention provides metal complexes having an activatingspecies with co-catalytic activity tethered to a multidentate ligandthat is coordinated to an active metal center of a metal complex.

In certain embodiments, the present invention provides unimolecularmetal complexes and methods for using the same in the copolymerizationof carbon dioxide and epoxides. In some embodiments, provided metalcomplexes have the structure:

wherein:

-   -   M is a metal atom;

comprises a multidentate ligand;

-   -   (Z)_(m) represents one or more activating moieties attached to        the multidentate ligand, where        is a linker moiety covalently coupled to the ligand, each Z is        an activating functional group; and m is an integer from 1 to 4        representing the number of Z groups present on an individual        linker moiety.

In some embodiments, tethered activating functional groups (Z) areneutral nitrogen-containing moieties. In certain embodiments, neutralnitrogen-containing moieties are selected from the group consisting of:

-   -   or a combination of two or more of these,        wherein:    -   each occurrence of R¹, and R² is independently hydrogen or an        optionally substituted radical selected from the group        consisting of C₁₋₂₀ aliphatic; C₁₋₂₀ heteroaliphatic; phenyl; a        3- to 8-membered saturated or partially unsaturated monocyclic        carbocycle, a 7-14 carbon saturated, partially unsaturated or        aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic        heteroaryl ring having 1-4 heteroatoms independently selected        from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated        or partially unsaturated heterocyclic ring having 1-3        heteroatoms independently selected from nitrogen, oxygen, or        sulfur; a 6- to 12-membered polycyclic saturated or partially        unsaturated heterocycle having 1-5 heteroatoms independently        selected from nitrogen, oxygen, or sulfur; or an 8- to        10-membered bicyclic heteroaryl ring having 1-5 heteroatoms        independently selected from nitrogen, oxygen, or sulfur; wherein        R¹ and R² groups can be taken together with intervening atoms to        form one or more optionally substituted rings optionally        containing one or more additional heteroatoms;    -   each occurrence of R⁵ is independently hydrogen or an optionally        substituted radical selected from the group consisting of C₁₋₂₀        aliphatic; C₁₋₂₀ heteroaliphatic; phenyl; a 3- to 8-membered        saturated or partially unsaturated monocyclic carbocycle, a 7-14        carbon saturated, partially unsaturated or aromatic polycyclic        carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having        1-4 heteroatoms independently selected from nitrogen, oxygen, or        sulfur; a 3- to 8-membered saturated or partially unsaturated        heterocyclic ring having 1-3 heteroatoms independently selected        from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic        saturated or partially unsaturated heterocycle having 1-5        heteroatoms independently selected from nitrogen, oxygen, or        sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having        1-5 heteroatoms independently selected from nitrogen, oxygen, or        sulfur; wherein an R⁵ group can be taken with an R¹ or R² group        to form one or more optionally substituted rings; and    -   each occurrence of R⁷ is independently hydrogen, a hydroxyl        protecting group, or an optionally substituted radical selected        from the group consisting of C₁₋₂₀ acyl; C₁₋₂₀ aliphatic; C₁₋₂₀        heteroaliphatic; phenyl; a 3- to 8-membered saturated or        partially unsaturated monocyclic carbocycle, a 7-14 carbon        saturated, partially unsaturated or aromatic polycyclic        carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having        1-4 heteroatoms independently selected from nitrogen, oxygen, or        sulfur; a 3- to 8-membered saturated or partially unsaturated        heterocyclic ring having 1-3 heteroatoms independently selected        from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic        saturated or partially unsaturated heterocycle having 1-5        heteroatoms independently selected from nitrogen, oxygen, or        sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having        1-5 heteroatoms independently selected from nitrogen, oxygen, or        sulfur.

In some embodiments, tethered activating functional groups (Z) arecationic moieties. In certain embodiments, cationic moieties areselected from the group consisting of:

or a combination of two or more of these,wherein:

-   -   each occurrence of R¹, R², and R³ is independently hydrogen or        an optionally substituted radical selected from the group        consisting of C₁₋₂₀ aliphatic; C₁₋₂₀ heteroaliphatic; phenyl; a        3- to 8-membered saturated or partially unsaturated monocyclic        carbocycle, a 7-14 carbon saturated, partially unsaturated or        aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic        heteroaryl ring having 1-4 heteroatoms independently selected        from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated        or partially unsaturated heterocyclic ring having 1-3        heteroatoms independently selected from nitrogen, oxygen, or        sulfur; a 6- to 12-membered polycyclic saturated or partially        unsaturated heterocycle having 1-5 heteroatoms independently        selected from nitrogen, oxygen, or sulfur; or an 8- to        10-membered bicyclic heteroaryl ring having 1-5 heteroatoms        independently selected from nitrogen, oxygen, or sulfur; wherein        any two or more R¹, R², and R³ groups can be taken together with        intervening atoms to form one or more optionally substituted        rings optionally containing one or more additional heteroatom s;    -   R⁴ is hydrogen or —OR⁷;    -   R^(4′) is hydrogen, hydroxyl, or optionally substituted C₁₋₂₀        aliphatic;    -   each occurrence of R⁵ and R⁶ is independently hydrogen or an        optionally substituted radical selected from the group        consisting of C₁₋₂₀ aliphatic; C₁₋₂₀ heteroaliphatic; phenyl; a        3- to 8-membered saturated or partially unsaturated monocyclic        carbocycle, a 7-14 carbon saturated, partially unsaturated or        aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic        heteroaryl ring having 1-4 heteroatoms independently selected        from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated        or partially unsaturated heterocyclic ring having 1-3        heteroatoms independently selected from nitrogen, oxygen, or        sulfur; a 6- to 12-membered polycyclic saturated or partially        unsaturated heterocycle having 1-5 heteroatoms independently        selected from nitrogen, oxygen, or sulfur; or an 8- to        10-membered bicyclic heteroaryl ring having 1-5 heteroatoms        independently selected from nitrogen, oxygen, or sulfur; wherein        R⁵ and R⁶ can be taken together with intervening atoms to form        one or more optionally substituted rings optionally containing        one or more heteroatoms, and an R⁵ or R⁶ group can be taken with        an R¹ or R² group to form one or more optionally substituted        rings;    -   each occurrence of R⁷ is independently hydrogen, a hydroxyl        protecting group, or an optionally substituted radical selected        from the group consisting of C₁₋₂₀ acyl; C₁₋₂₀ aliphatic; C₁₋₂₀        heteroaliphatic; phenyl; a 3- to 8-membered saturated or        partially unsaturated monocyclic carbocycle, a 7-14 carbon        saturated, partially unsaturated or aromatic polycyclic        carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having        1-4 heteroatoms independently selected from nitrogen, oxygen, or        sulfur; a 3- to 8-membered saturated or partially unsaturated        heterocyclic ring having 1-3 heteroatoms independently selected        from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic        saturated or partially unsaturated heterocycle having 1-5        heteroatoms independently selected from nitrogen, oxygen, or        sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having        1-5 heteroatoms independently selected from nitrogen, oxygen, or        sulfur;    -   each occurrence of R⁸, R⁹, and R¹⁰ is independently hydrogen or        an optionally substituted radical selected from the group        consisting of C₁₋₂₀ aliphatic; C₁₋₂₀ heteroaliphatic; phenyl; a        3- to 8-membered saturated or partially unsaturated monocyclic        carbocycle, a 7-14 carbon saturated, partially unsaturated or        aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic        heteroaryl ring having 1-4 heteroatoms independently selected        from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated        or partially unsaturated heterocyclic ring having 1-3        heteroatoms independently selected from nitrogen, oxygen, or        sulfur; a 6- to 12-membered polycyclic saturated or partially        unsaturated heterocycle having 1-5 heteroatoms independently        selected from nitrogen, oxygen, or sulfur; or an 8- to        10-membered bicyclic heteroaryl ring having 1-5 heteroatoms        independently selected from nitrogen, oxygen, or sulfur; wherein        any two or more R⁸, R⁹ and R¹⁰ groups can be taken together with        intervening atoms to form one or more optionally substituted        rings;    -   each occurrence of R¹¹ is independently selected from the group        consisting of: halogen, —NO₂, —CN, —SR^(y), —S(O)R^(y),        —S(O)₂R^(y), —NR^(y)C(O)R^(y), —OC(O)R^(y), —CO₂R^(y), —NCO,        —N₃, —OR⁷, —OC(O)N(R^(y))₂, —N(R^(y))₂, —NR^(y)C(O)R^(y),        —NR^(y)C(O)OR^(y); or an optionally substituted radical selected        from the group consisting of C₁₋₂₀ aliphatic; C₁₋₂₀        heteroaliphatic; phenyl; a 3- to 8-membered saturated or        partially unsaturated monocyclic carbocycle, a 7-14 carbon        saturated, partially unsaturated or aromatic polycyclic        carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having        1-4 heteroatoms independently selected from nitrogen, oxygen, or        sulfur; a 3- to 8-membered saturated or partially unsaturated        heterocyclic ring having 1-3 heteroatoms independently selected        from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic        saturated or partially unsaturated heterocycle having 1-5        heteroatoms independently selected from nitrogen, oxygen, or        sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having        1-5 heteroatoms independently selected from nitrogen, oxygen, or        sulfur; where each occurrence of R^(y) is independently —H, or        an optionally substituted radical selected from the group        consisting of C₁₋₆ aliphatic, 3- to 7-membered heterocyclic,        phenyl, and 8- to 10-membered aryl, and where two or more        adjacent R¹¹ groups can be taken together to form an optionally        substituted saturated, partially unsaturated, or aromatic 5- to        12-membered ring containing 0 to 4 heteroatoms;    -   X⁻ is any anion, and    -   Ring A is an optionally substituted, 5- to 10-membered        heteroaryl group.

In some embodiments, an activating functional group (Z) is aphosphorous-containing functional group.

In certain embodiments, a phosphorous-containing functional group ischosen from the group consisting of: phosphines (—PR^(y) ₂); Phosphineoxides —P(O)R^(y) ₂; phosphinites P(OR⁷)R^(y) ₂; phosphonitesP(OR⁷)₂R^(y); phosphites P(OR⁷)₃; phosphinates OP(OR⁷)R^(y) ₂;phosphonates; OP(OR⁷)₂R^(y); phosphates —OP(OR⁷)₃; phosponium salts([—PR^(y) ₃]⁻) where the phosphorous-containing functional group may belinked to a metal complex through any available position (e.g. directlinkage via the phosphorous atom, or in some cases via an oxygen atom).

In certain embodiments, a phosphorous-containing functional group ischosen from the group consisting of:

or a combination of two or more of these

-   -   wherein R¹², are as defined above; and    -   each R^(7′) is independently hydrogen, a hydroxyl protecting        group, or an optionally substituted radical selected from the        group consisting of C₁₋₂₀ acyl; C₁₋₂₀ aliphatic; C₁₋₂₀        heteroaliphatic; phenyl; a 3- to 8-membered saturated or        partially unsaturated monocyclic carbocycle, a 7-14 carbon        saturated, partially unsaturated or aromatic polycyclic        carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having        1-4 heteroatoms independently selected from nitrogen, oxygen, or        sulfur; a 3- to 8-membered saturated or partially unsaturated        heterocyclic ring having 1-3 heteroatoms independently selected        from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic        saturated or partially unsaturated heterocycle having 1-5        heteroatoms independently selected from nitrogen, oxygen, or        sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having        1-5 heteroatoms independently selected from nitrogen, oxygen, or        sulfur; and where two R^(7′) groups can be taken together with        intervening atoms to form an optionally substituted ring        optionally containing one or more heteroatoms, and an R^(7′)        group can be taken with an R¹ or R² group to an optionally        substituted ring;

In some embodiments, phosphorous containing functional groups includethose disclosed in The Chemistry of Organophosphorus Compounds. Volume4. Ter-and Quinquevalent Phosphorus Acids and their Derivatives. TheChemistry of Functional Group Series Edited by Frank R. Hartley(Cranfield University, Cranfield, U.K.). Wiley: New York. 1996. ISBN0-471-95706-2, the entirety of which is hereby incorporated herein byreference.

In certain embodiments, a phosphorous-containing functional group hasthe structure*—(X)_(b)—[(R⁶R⁷R⁸P)⁺]_(n)Q^(n-), wherein:

-   X is —O—, —N═, or —NR^(z),-   b is 1 or 0,-   each of R⁶, R⁷ and R⁸ are independently present or absent and, if    present, are independently selected from the group consisting of    optionally substituted C₁-C₂₀ aliphatic, optionally substituted    C₆₋C₁₄ aryl, optionally substituted 3- to 14-membered heterocyclic,    optionally substituted 5- to 14-membered heteroaryl, halogen, ═O,    —OR^(z), ═NR^(z), and N(R^(z))₂ where R^(z) is hydrogen, or an    optionally substituted C₁-C₂₀ aliphatic, optionally substituted 6-    to 14-membered aryl, optionally substituted 3- to 14-membered    heterocyclic, or optionally substituted 5- to 14-membered    heteroaryl,-   Q is any anion, and-   n is an integer between 1 and 4.

In some embodiments, the present disclosure encompasses methods for thecopolymerization of epoxides and carbon dioxide, such methods comprisingcontacting one or more epoxides with a catalyst described above in thepresence of carbon dioxide.

In some embodiments, the present disclosure encompasses methods for theformation of cyclic carbonates from epoxides and carbon dioxide, suchmethods comprising contacting one or more epoxides with a catalystdescribed above in the presence of carbon dioxide.

In some embodiments, the present disclosure encompasses methods for theformation of polyethers, such methods comprising contacting one or moreepoxides with a catalyst described above.

Definitions

Definitions of specific functional groups and chemical terms aredescribed in more detail below. For purposes of this invention, thechemical elements are identified in accordance with the Periodic Tableof the Elements, CAS version, Handbook of Chemistry and Physics, 75^(th)Ed., inside cover, and specific functional groups are generally definedas described therein. Additionally, general principles of organicchemistry, as well as specific functional moieties and reactivity, aredescribed in Organic Chemistry, Thomas Sorrell, University ScienceBooks, Sausalito, 1999; Smith and March March's Advanced OrganicChemistry, 5^(th) Edition, John Wiley & Sons, Inc., New York, 2001;Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., NewYork, 1989; Carruthers, Some Modern Methods of Organic Synthesis, 3^(rd)Edition, Cambridge University Press, Cambridge, 1987; the entirecontents of each of which are incorporated herein by reference.

Certain compounds of the present invention can comprise one or moreasymmetric centers, and thus can exist in various stereoisomeric forms,e.g., enantiomers and/or diastereomers. Thus, inventive compounds andcompositions thereof may be in the form of an individual enantiomer,diastereomer or geometric isomer, or may be in the form of a mixture ofstereoisomers. In certain embodiments, the compounds of the inventionare enantiopure compounds. In certain embodiments, mixtures ofenantiomers or diastereomers are provided.

Furthermore, certain compounds, as described herein may have one or moredouble bonds that can exist as either a Z or E isomer, unless otherwiseindicated. The invention additionally encompasses the compounds asindividual isomers substantially free of other isomers andalternatively, as mixtures of various isomers, e.g., racemic mixtures ofenantiomers. In addition to the above-mentioned compounds per se, thisinvention also encompasses compositions comprising one or morecompounds.

As used herein, the term “isomers” includes any and all geometricisomers and stereoisomers. For example, “isomers” include cis- andtrans-isomers, E- and Z-isomers, R- and S-enantiomers, diastereomers,(D)-isomers, (L)-isomers, racemic mixtures thereof, and other mixturesthereof, as falling within the scope of the invention. For instance, acompound may, in some embodiments, be provided substantially free of oneor more corresponding stereoisomers, and may also be referred to as“stereochemically enriched.”

Where a particular enantiomer is preferred, it may, in some embodimentsbe provided substantially free of the opposite enantiomer, and may alsobe referred to as “optically enriched.” “Optically enriched,” as usedherein, means that the compound is made up of a significantly greaterproportion of one enantiomer. In certain embodiments the compound ismade up of at least about 90% by weight of an enantiomer. In someembodiments the compound is made up of at least about 95%, 97%, 98%,99%, 99.5%, 99.7%, 99.8%, or 99.9% by weight of an enantiomer. In someembodiments the enantiomeric excess of provided compounds is at leastabout 90%, 95%, 97%, 98%, 99%, 99.5%, 99.7%, 99.8%, or 99.9%. In someembodiments, enantiomers may be isolated from racemic mixtures by anymethod known to those skilled in the art, including chiral high pressureliquid chromatography (HPLC) and the formation and crystallization ofchiral salts or prepared by asymmetric syntheses. See, for example,Jacques, et al., Enantiomers, Racemates and Resolutions (WileyInterscience, New York, 1981); Wilen, S. H., et al., Tetrahedron 33:2725(1977); Eliel, E. L. Stereochemistry of Carbon Compounds (McGraw-Hill, NY, 1962); Wilen, S. H. Tables of Resolving Agents and OpticalResolutions p. 268 (E. L. Eliel, Ed., Univ. of Notre Dame Press, NotreDame, Ind. 1972).

The terms “halo” and “halogen” as used herein refer to an atom selectedfrom fluorine (fluoro, —F), chlorine (chloro, —Cl), bromine (bromo,—Br), and iodine (iodo, —I).

The term “aliphatic” or “aliphatic group”, as used herein, denotes ahydrocarbon moiety that may be straight-chain (i.e., unbranched),branched, or cyclic (including fused, bridging, and spiro-fusedpolycyclic) and may be completely saturated or may contain one or moreunits of unsaturation, but which is not aromatic. Unless otherwisespecified, aliphatic groups contain 1-30 carbon atoms. In certainembodiments, aliphatic groups contain 1-12 carbon atoms. In certainembodiments, aliphatic groups contain 1-8 carbon atoms. In certainembodiments, aliphatic groups contain 1-6 carbon atoms. In someembodiments, aliphatic groups contain 1-5 carbon atoms, in someembodiments, aliphatic groups contain 1-4 carbon atoms, in yet otherembodiments aliphatic groups contain 1-3 carbon atoms, and in yet otherembodiments aliphatic groups contain 1-2 carbon atoms. Suitablealiphatic groups include, but are not limited to, linear or branched,alkyl, alkenyl, and alkynyl groups, and hybrids thereof such as(cycloalkyl)alkyl, (cycloalkenyl)alkyl or (cycloalkyl)alkenyl. Incertain embodiments, the term aliphatic group encompasses aliphaticgroups wherein one or more hydrogen atoms are replaced with a halogenatom. In certain embodiments, the term aliphatic group encompasseschlorinated or fluorinated aliphatic groups including perfluorinatedcompounds.

The term “epoxide”, as used herein, refers to a substituted orunsubstituted oxirane. Such substituted oxiranes include monosubstitutedoxiranes, disubstituted oxiranes, trisubstituted oxiranes, andtetrasubstituted oxiranes. Such epoxides may be further optionallysubstituted as defined herein. In certain embodiments, epoxides comprisea single oxirane moiety. In certain embodiments, epoxides comprise twoor more oxirane moieties.

The term “polymer”, as used herein, refers to a molecule of highrelative molecular mass, the structure of which comprises the multiplerepetition of units derived, actually or conceptually, from molecules oflow relative molecular mass. In certain embodiments, a polymer iscomprised of only one monomer species (e.g., polyethylene oxide). Incertain embodiments, a polymer of the present invention is a copolymer,terpolymer, heteropolymer, block copolymer, or tapered heteropolymer ofone or more epoxides.

The term “unsaturated”, as used herein, means that a moiety has one ormore double or triple bonds.

The terms “cycloaliphatic”, “carbocycle”, or “carbocyclic”, used aloneor as part of a larger moiety, refer to a saturated or partiallyunsaturated cyclic aliphatic monocyclic, bicyclic, or polycyclic ringsystems, as described herein, having from 3 to 12 members, wherein thealiphatic ring system is optionally substituted as defined above anddescribed herein. Cycloaliphatic groups include, without limitation,cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl,cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, andcyclooctadienyl. In some embodiments, the cycloalkyl has 3-6 carbons.The terms “cycloaliphatic”, “carbocycle” or “carbocyclic” also includealiphatic rings that are fused to one or more aromatic or nonaromaticrings, such as decahydronaphthyl or tetrahydronaphthyl, where theradical or point of attachment is on the aliphatic ring. In someembodiments, a carbocyclic groups is bicyclic. In some embodiments, acarbocyclic group is tricyclic. In some embodiments, a carbocyclic groupis polycyclic.

The term “alkyl,” as used herein, refers to saturated, straight- orbranched-chain hydrocarbon radicals derived by removal of a singlehydrogen atom from an aliphatic moiety. Unless otherwise specified,alkyl groups contain 1-12 carbon atoms. In certain embodiments, alkylgroups contain 1-8 carbon atoms. In certain embodiments, alkyl groupscontain 1-6 carbon atoms. In some embodiments, alkyl groups contain 1-5carbon atoms, in some embodiments, alkyl groups contain 1-4 carbonatoms, in yet other embodiments alkyl groups contain 1-3 carbon atoms,and in yet other embodiments alkyl groups contain 1-2 carbon atoms.Examples of alkyl radicals include, but are not limited to, methyl,ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, sec-pentyl,iso-pentyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, sec-hexyl,n-heptyl, n-octyl, n-decyl, n-undecyl, dodecyl, and the like.

The term “alkenyl,” as used herein, denotes a monovalent group derivedby the removal of a single hydrogen atom from a straight- orbranched-chain aliphatic moiety having at least one carbon-carbon doublebond. Unless otherwise specified, alkenyl groups contain 2-12 carbonatoms. In certain embodiments, alkenyl groups contain 2-8 carbon atoms.In certain embodiments, alkenyl groups contain 2-6 carbon atoms. In someembodiments, alkenyl groups contain 2-5 carbon atoms, in someembodiments, alkenyl groups contain 2-4 carbon atoms, in yet otherembodiments alkenyl groups contain 2-3 carbon atoms, and in yet otherembodiments alkenyl groups contain 2 carbon atoms. Alkenyl groupsinclude, for example, ethenyl, propenyl, allyl, 1,3-butadienyl, butenyl,1-methyl-2-buten-1-yl, allyl, 1,3-butadienyl, allenyl, and the like.

The term “alkynyl,” as used herein, refers to a monovalent group derivedby the removal of a single hydrogen atom from a straight- orbranched-chain aliphatic moiety having at least one carbon-carbon triplebond. Unless otherwise specified, alkynyl groups contain 2-12 carbonatoms. In certain embodiments, alkynyl groups contain 2-8 carbon atoms.In certain embodiments, alkynyl groups contain 2-6 carbon atoms. In someembodiments, alkynyl groups contain 2-5 carbon atoms, in someembodiments, alkynyl groups contain 2-4 carbon atoms, in yet otherembodiments alkynyl groups contain 2-3 carbon atoms, and in yet otherembodiments alkynyl groups contain 2 carbon atoms. Representativealkynyl groups include, but are not limited to, ethynyl, 2-propynyl(propargyl), 1-propynyl, and the like.

The term “carbocycle” and “carbocyclic ring” as used herein, refer tomonocyclic and polycyclic moieties wherein the rings contain only carbonatoms. Unless otherwise specified, carbocycles may be saturated,partially unsaturated or aromatic, and contain 3 to 20 carbon atoms.Representative carbocyles include cyclopropane, cyclobutane,cyclopentane, cyclohexane, bicyclo[2,2,1]heptane, norbornene, phenyl,cyclohexene, naphthalene, and spiro[4.5]decane, to name but a few.

The term “aryl” used alone or as part of a larger moiety as in“aralkyl”, “aralkoxy”, or “aryloxyalkyl”, refers to monocyclic andpolycyclic ring systems having a total of six to 20 ring members,wherein at least one ring in the system is aromatic and wherein eachring in the system contains three to twelve ring members. The term“aryl” may be used interchangeably with the term “aryl ring”. In certainembodiments of the present invention, “aryl” refers to an aromatic ringsystem which includes, but is not limited to, phenyl, biphenyl,naphthyl, anthracyl and the like, which may bear one or moresubstituents. Also included within the scope of the term “aryl”, as itis used herein, is a group in which an aromatic ring is fused to one ormore additional rings, such as benzofuranyl, indanyl, phthalimidyl,naphthimidyl, phenantriidinyl, or tetrahydronaphthyl, and the like.

The term “heteroaliphatic,” as used herein, refers to aliphatic groupswherein one or more carbon atoms are independently replaced by one ormore atoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, or boron. In certain embodiments, one to sixcarbon atoms are independently replaced by one or more of oxygen,sulfur, nitrogen, or phosphorus. Heteroaliphatic groups may besubstituted or unsubstituted, branched or unbranched, cyclic or acyclic,and include saturated, unsaturated or partially unsaturated groups.

The terms “heteroaryl” and “heteroar-”, used alone or as part of alarger moiety, e.g., “heteroaralkyl”, or “heteroaralkoxy”, refer togroups having 5 to 14 ring atoms, preferably 5, 6, or 9 ring atoms;having 6, 10, or 14 π electrons shared in a cyclic array; and having, inaddition to carbon atoms, from one to five heteroatoms. The term“heteroatom” refers to nitrogen, oxygen, or sulfur, and includes anyoxidized form of nitrogen or sulfur, and any quaternized form of a basicnitrogen. Heteroaryl groups include, without limitation, thienyl,furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl,oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl,thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl,purinyl, naphthyridinyl, benzofuranyl and pteridinyl. The terms“heteroaryl” and “heteroar-”, as used herein, also include groups inwhich a heteroaromatic ring is fused to one or more aryl,cycloaliphatic, or heterocyclyl rings, where the radical or point ofattachment is on the heteroaromatic ring. Nonlimiting examples includeindolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl,indazolyl, benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl,cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl,carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl,tetrahydroquinolinyl, tetrahydroisoquinolinyl, andpyrido[2,3-b]-1,4-oxazin-3(4H)-one. A heteroaryl group may be mono- orpolycyclic. The term “heteroaryl” may be used interchangeably with theterms “heteroaryl ring”, “heteroaryl group”, or “heteroaromatic”, any ofwhich terms include rings that are optionally substituted. The term“heteroaralkyl” refers to an alkyl group substituted by a heteroaryl,wherein the alkyl and heteroaryl portions independently are optionallysubstituted.

As used herein, the terms “heterocycle”, “heterocyclyl”, “heterocyclicradical”, and “heterocyclic ring” are used interchangeably and refer toa stable 5- to 7-membered monocyclic or 7-14-membered bicyclicheterocyclic moiety that is saturated, partially unsaturated, oraromatic and having, in addition to carbon atoms, one or more,preferably one to four, heteroatoms, as defined above. When used inreference to a ring atom of a heterocycle, the term “nitrogen” includesa substituted nitrogen. As an example, in a saturated or partiallyunsaturated ring having 0-3 heteroatoms selected from oxygen, sulfur ornitrogen, the nitrogen may be N (as in 3,4-dihydro-2H-pyrrolyl), NH (asin pyrrolidinyl), or +NR (as in N-substituted pyrrolidinyl).

A heterocyclic ring can be attached to its pendant group at anyheteroatom or carbon atom that results in a stable structure and any ofthe ring atoms can be optionally substituted. Examples of such saturatedor partially unsaturated heterocyclic radicals include, withoutlimitation, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl,pyrrolidonyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl,tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl,dioxanyl, dioxolanyl, diazepinyl, oxazepinyl, thiazepinyl, morpholinyl,and quinuclidinyl. The terms “heterocycle”, “heterocyclyl”,“heterocyclyl ring”, “heterocyclic group”, “heterocyclic moiety”, and“heterocyclic radical”, are used interchangeably herein, and alsoinclude groups in which a heterocyclyl ring is fused to one or morearyl, heteroaryl, or cycloaliphatic rings, such as indolinyl,3H-indolyl, chromanyl, phenanthridinyl, or tetrahydroquinolinyl, wherethe radical or point of attachment is on the heterocyclyl ring. Aheterocyclyl group may be mono- or bicyclic. The term“heterocyclylalkyl” refers to an alkyl group substituted by aheterocyclyl, wherein the alkyl and heterocyclyl portions independentlyare optionally substituted.

The term “acyl” as used herein refers to a group having a formula —C(O)Rwhere R is hydrogen or an optionally substituted aliphatic, aryl, orheterocyclic group.

As used herein, the term “partially unsaturated” refers to a ring moietythat includes at least one double or triple bond. The term “partiallyunsaturated” is intended to encompass rings having multiple sites ofunsaturation, but is not intended to include aryl or heteroarylmoieties, as herein defined.

One of ordinary skill in the art will appreciate that the syntheticmethods, as described herein, utilize a variety of protecting groups. Bythe term “protecting group,” as used herein, it is meant that aparticular functional moiety, e.g., O, S, or N, is masked or blocked,permitting, if desired, a reaction to be carried out selectively atanother reactive site in a multifunctional compound. In preferredembodiments, a protecting group reacts selectively in good yield to givea protected substrate that is stable to the projected reactions; theprotecting group is preferably selectively removable by readilyavailable, preferably non-toxic reagents that do not attack the otherfunctional groups; the protecting group forms a separable derivative(more preferably without the generation of new stereogenic centers); andthe protecting group will preferably have a minimum of additionalfunctionality to avoid further sites of reaction. As detailed herein,oxygen, sulfur, nitrogen, and carbon protecting groups may be utilized.By way of non-limiting example, hydroxyl protecting groups includemethyl, methoxylmethyl (MOM), methylthiomethyl (MTM), t-butylthiomethyl,(phenyldimethylsilyl)methoxymethyl (SMOM), benzyloxymethyl (BOM),p-methoxybenzyloxymethyl (PMBM), (4-methoxyphenoxy)methyl (p-AOM),guaiacolmethyl (GUM), t-butoxymethyl, 4-pentenyloxymethyl (POM),siloxymethyl, 2-methoxyethoxymethyl (MEM), 2,2,2-trichloroethoxymethyl,bis(2-chloroethoxy)methyl, 2-(trimethylsilyl)ethoxymethyl (SEMOR),tetrahydropyranyl (THP), 3-bromotetrahydropyranyl,tetrahydrothiopyranyl, 1-methoxycyclohexyl, 4-methoxytetrahydropyranyl(MTHP), 4-methoxytetrahydrothiopyranyl, 4-methoxytetrahydrothiopyranylS,S-dioxide, 1-[(2-chloro-4-methyl)phenyl]-4-methoxypiperidin-4-yl(CTMP), 1,4-dioxan-2-yl, tetrahydrofuranyl, tetrahydrothiofuranyl,2,3,3a,4,5,6,7,7a-octahydro-7,8,8-trimethyl-4,7-methanobenzofuran-2-yl,1-ethoxyethyl, 1-(2-chloroethoxy)ethyl, 1-methyl-1-methoxyethyl,1-methyl-1-benzyloxyethyl, 1-methyl-1-benzyloxy-2-fluoroethyl,2,2,2-trichloroethyl, 2-trimethylsilylethyl, 2-(phenylselenyl)ethyl,t-butyl, allyl, p-chlorophenyl, p-methoxyphenyl, 2,4-dinitrophenyl,benzyl, p-methoxybenzyl, 3,4-dimethoxybenzyl, o-nitrobenzyl,p-nitrobenzyl, p-halobenzyl, 2,6-dichlorobenzyl, p-cyanobenzyl,p-phenylbenzyl, 2-picolyl, 4-picolyl, 3-methyl-2-picolyl N-oxido,diphenylmethyl, p,p′-dinitrobenzhydryl, 5-dibenzosuberyl,triphenylmethyl, α-naphthyldiphenylmethyl,p-methoxyphenyldiphenylmethyl, di(p-methoxyphenyl)phenylmethyl,tri(p-methoxyphenyl)methyl, 4-(4′-bromophenacyloxyphenyl)diphenylmethyl,4,4′,4″-tris(4,5-dichlorophthalimidophenyl)methyl, 4,4′,4‘’-tris(levulinoyloxyphenyl)methyl, 4,4′,4‘’-tris(benzoyloxyphenyl)methyl,3-(imidazol-1-yl)bis(4′,4″-dimethoxyphenyl)methyl,1,1-bis(4-methoxyphenyl)-1′-pyrenylmethyl, 9-anthryl,9-(9-phenyl)xanthenyl, 9-(9-phenyl-10-oxo)anthryl,1,3-benzodithiolan-2-yl, benzisothiazolyl S,S-dioxido, trimethylsilyl(TMS), triethylsilyl (TES), triisopropylsilyl (TIPS),dimethylisopropylsilyl (IPDMS), diethylisopropylsilyl (DEIPS),dimethylthexylsilyl, t-butyldimethylsilyl (TBDMS), t-butyldiphenylsilyl(TBDPS), tribenzylsilyl, tri-p-xylylsilyl, triphenylsilyl,diphenylmethylsilyl (DPMS), t-butylmethoxyphenylsilyl (TBMPS), formate,benzoylformate, acetate, chloroacetate, dichloroacetate,trichloroacetate, trifluoroacetate, methoxyacetate,triphenylmethoxyacetate, phenoxyacetate, p-chlorophenoxyacetate,3-phenylpropionate, 4-oxopentanoate (levulinate),4,4-(ethylenedithio)pentanoate (levulinoyldithioacetal), pivaloate,adamantoate, crotonate, 4-methoxycrotonate, benzoate, p-phenylbenzoate,2,4,6-trimethylbenzoate (mesitoate), alkyl methyl carbonate,9-fluorenylmethyl carbonate (Fmoc), alkyl ethyl carbonate, alkyl2,2,2-trichloroethyl carbonate (Troc), 2-(trimethylsilyl)ethyl carbonate(TMSEC), 2-(phenylsulfonyl) ethyl carbonate (Psec),2-(triphenylphosphonio) ethyl carbonate (Peoc), alkyl isobutylcarbonate, alkyl vinyl carbonate alkyl allyl carbonate, alkylp-nitrophenyl carbonate, alkyl benzyl carbonate, alkyl p-methoxybenzylcarbonate, alkyl 3,4-dimethoxybenzyl carbonate, alkyl o-nitrobenzylcarbonate, alkyl p-nitrobenzyl carbonate, alkyl S-benzyl thiocarbonate,4-ethoxy-1-napththyl carbonate, methyl dithiocarbonate, 2-iodobenzoate,4-azidobutyrate, 4-nitro-4-methylpentanoate, o-(dibromomethyl)benzoate,2-formylbenzenesulfonate, 2-(methylthiomethoxy)ethyl,4-(methylthiomethoxy)butyrate, 2-(methylthiomethoxymethyl)benzoate,2,6-dichloro-4-methylphenoxyacetate,2,6-dichloro-4-(1,1,3,3-tetramethylbutyl)phenoxyacetate,2,4-bis(1,1-dimethylpropyl)phenoxyacetate, chlorodiphenylacetate,isobutyrate, monosuccinoate, (E)-2-methyl-2-butenoate,o-(methoxycarbonyl)benzoate, α-naphthoate, nitrate, alkylN,N,N′,N′-tetramethylphosphorodiamidate, alkyl N-phenylcarbamate,borate, dimethylphosphinothioyl, alkyl 2,4-dinitrophenylsulfenate,sulfate, methanesulfonate (mesylate), benzylsulfonate, and tosylate(Ts). For protecting 1,2- or 1,3-diols, the protecting groups includemethylene acetal, ethylidene acetal, 1-t-butylethylidene ketal,1-phenylethylidene ketal, (4-methoxyphenyl)ethylidene acetal,2,2,2-trichloroethylidene acetal, acetonide, cyclopentylidene ketal,cyclohcxylidene ketal, cycloheptylidene ketal, benzylidene acetal,p-methoxybenzylidene acetal, 2,4-dimethoxybenzylidene ketal,3,4-dimethoxybenzylidene acetal, 2-nitrobenzylidene acetal,methoxymethylene acetal, ethoxymethylene acetal, dimethoxymethyleneortho ester, 1-methoxyethylidene ortho ester, 1-ethoxyethylidine orthoester, 1,2-dimethoxyethylidene ortho ester, α-methoxybenzylidene orthoester, 1-(N,N-dimethylamino)ethylidene derivative,α-(N,N′-dimethylamino)benzylidene derivative, 2-oxacyclopentylideneortho ester, di-t-butylsilylene group (DTBS),1,3-(1,1,3,3-tetraisopropyldisiloxanylidene) derivative (TIPDS),tetra-t-butoxydisiloxane-1,3-diylidene derivative (TBDS), cycliccarbonates, cyclic boronates, ethyl boronate, and phenyl boronate.Amino-protecting groups include methyl carbamate, ethyl carbamate,9-fluorenylmethyl carbamate (Fmoc), 9-(2-sulfo)fluorenylmethylcarbamate, 9-(2,7-dibromo)fluoroenylmethyl carbamate,2,7-di-t-butyl-[9-(10,10-dioxo-10,10,10,10-tetrahydrothioxanthyl)]methylcarbamate (DBD-Tmoc), 4-methoxyphenacyl carbamate (Phenoc),2,2,2-trichloroethyl carbamate (Troc), 2-trimethylsilylethyl carbamate(Teoc), 2-phenylethyl carbamate (hZ), 1-(1-adamantyl)-1-methylethylcarbamate (Adpoc), 1,1-dimethyl-2-haloethyl carbamate,1,1-dimethyl-2,2-dibromoethyl carbamate (DB-t-BOC),1,1-dimethyl-2,2,2-trichloroethyl carbamate (TCBOC),1-methyl-1-(4-biphenylyl)ethyl carbamate (Bpoc),1-(3,5-di-t-butylphenyl)-1-methylethyl carbamate (t-Bumeoc), 2-(2′- and4′-pyridyl)ethyl carbamate (Pyoc), 2-(N, N-dicyclohexylcarboxamido)ethylcarbamate, t-butyl carbamate (BOC), 1-adamantyl carbamate (Adoc), vinylcarbamate (Voc), allyl carbamate (Alloc), 1-isopropylallyl carbamate(Ipaoc), cinnamyl carbamate (Coc), 4-nitrocinnamyl carbamate (Noc),8-quinolyl carbamate, N-hydroxypiperidinyl carbamate, alkyldithiocarbamate, benzyl carbamate (Cbz), p-methoxybenzyl carbamate (Moz),p-nitobenzyl carbamate, p-bromobenzyl carbamate, p-chlorobenzylcarbamate, 2,4-dichlorobenzyl carbamate, 4-methylsulfinylbenzylcarbamate (Msz), 9-anthrylmethyl carbamate, diphenylmethyl carbamate,2-methylthioethyl carbamate, 2-methylsulfonylethyl carbamate,2-(p-toluenesulfonyl)ethyl carbamate, [2-(1,3-dithianyl)]methylcarbamate (Dmoc), 4-methylthiophenyl carbamate (Mtpc),2,4-dimethylthiophenyl carbamate (Bmpc), 2-phosphonioethyl carbamate(Peoc), 2-triphenylphosphonioisopropyl carbamate (Ppoc),1,1-dimethyl-2-cyanoethyl carbamate, m-chloro-p-acyloxybenzyl carbamate,p-(dihydroxyboryl)benzyl carbamate, 5-benzisoxazolylmethyl carbamate,2-(trifluoromethyl)-6-chromonylmethyl carbamate (Tcroc), m-nitrophenylcarbamate, 3,5-dimethoxybenzyl carbamate, o-nitrobenzyl carbamate,3,4-dimethoxy-6-nitrobenzyl carbamate, phenyl(o-nitrophenyl)methylcarbamate, phenothiazinyl-(10)-carbonyl derivative,N′-p-toluenesulfonylaminocarbonyl derivative, N′-phenylaminothiocarbonylderivative, t-amyl carbamate, S-benzyl thiocarbamate, p-cyanobenzylcarbamate, cyclobutyl carbamate, cyclohexyl carbamate, cyclopentylcarbamate, cyclopropylmethyl carbamate, p-decyloxybenzyl carbamate,2,2-dimethoxycarbonylvinyl carbamate, o-(N,N-dimethylcarboxamido)benzylcarbamate, 1,1-dimethyl-3-(N,N-dimethylcarboxamido)propyl carbamate,1,1-dimethylpropynyl carbamate, di(2-pyridyl)methyl carbamate,2-furanylmethyl carbamate, 2-iodoethyl carbamate, isoborynl carbamate,isobutyl carbamate, isonicotinyl carbamate,p-(p′-methoxyphenylazo)benzyl carbamate, 1-methylcyclobutyl carbamate,1-methylcyclohexyl carbamate, 1-methyl-1-cyclopropylmethyl carbamate,1-methyl-1-(3,5-dimethoxyphenyl)ethyl carbamate,1-methyl-1-(p-phenylazophenyl)ethyl carbamate, 1-methyl-1-phenylethylcarbamate, 1-methyl-1-(4-pyridyl)ethyl carbamate, phenyl carbamate,p-(phenylazo)benzyl carbamate, 2,4,6-tri-t-butylphenyl carbamate,4-(trimethylammonium)benzyl carbamate, 2,4,6-trimethylbenzyl carbamate,formamide, acetamide, chloroacetamide, trichloroacetamide,trifluoroacetamide, phenylacetamide, 3-phenylpropanamide, picolinamide,3-pyridylcarboxamide, N-benzoylphenylalanyl derivative, benzamide,p-phenylbenzamide, o-nitophenylacetamide, o-nitrophenoxyacetamide,acetoacetamide, (N′-dithiobenzyloxycarbonylamino)acetamide,3-(p-hydroxyphenyl)propanamide, 3-(o-nitrophenyl)propanamide,2-methyl-2-(o-nitrophenoxy)propanamide,2-methyl-2-(o-phenylazophenoxy)propanamide, 4-chlorobutanamide,3-methyl-3-nitrobutanamide, o-nitrocinnamide, N-acetylmethioninederivative, o-nitrobenzamide, o-(benzoyloxymethyl)benzamide,4,5-diphenyl-3-oxazolin-2-one, N-phthalimide, N-dithiasuccinimide (Dts),N-2,3-diphenylmaleimide, N-2,5-dimethylpyrrole,N-1,1,4,4-tetramethyldisilylazacyclopentane adduct (STABASE),5-substituted 1,3-dimethyl-1,3,5-triazacyclohexan-2-one, 5-substituted1,3-dibenzyl-1,3,5-triazacyclohexan-2-one, 1-substituted3,5-dinitro-4-pyridone, N-methylamine, N-allylamine,N-[2-(trimethylsilyl)ethoxy]methylamine (SEM), N-3-acetoxypropylamine,N-(1-isopropyl-4-nitro-2-oxo-3-pyroolin-3-yl)amine, quaternary ammoniumsalts, N-benzylamine, N-di(4-methoxyphenyl)methylamine,N-5-dibenzosuberylamine, N-triphenylmethylamine (Tr),N-[(4-methoxyphenyl)diphenylmethyl]amine (MMTr),N-9-phenylfluorenylamine (PhF),N-2,7-dichloro-9-fluorenylmethyleneamine, N-ferrocenylmethylamino (Fcm),N-2-picolylamino N′-oxide, N-1,1-dimethylthiomethyleneamine,N-benzylideneamine, N-p-methoxybenzylideneamine,N-diphenylmethyleneamine, N-[(2-pyridyl)mesityl]methyleneamine,N—(N′,N′-dimethylaminomethylene)amine, N,N′-isopropylidenediamine,N-p-nitrobenzylideneamine, N-salicylideneamine,N-5-chlorosalicylideneamine,N-(5-chloro-2-hydroxyphenyl)phenylmethyleneamine,N-cyclohexylideneamine, N-(5,5-dimethyl-3-oxo-1-cyclohexenyl)amine,N-borane derivative, N-diphenylborinic acid derivative,N-[phenyl(pentacarbonylchromium- or tungsten)carbonyl]amine, N-copperchelate, N-zinc chelate, N-nitroamine, N-nitrosoamine, amine N-oxide,diphenylphosphinamide (Dpp), dimethylthiophosphinamide (Mpt),diphenylthiophosphinamide (Ppt), dialkyl phosphoramidates, dibenzylphosphoramidate, diphenyl phosphoramidate, benzenesulfenamide,o-nitrobenzenesulfenamide (Nps), 2,4-dinitrobenzenesulfenamide,pentachlorobenzenesulfenamide, 2-nitro-4-methoxybenzenesulfenamide,triphenylmethylsulfenamide, 3-nitropyridinesulfenamide (Npys),p-toluenesulfonamide (Ts), benzenesulfonamide,2,3,6,-trimethyl-4-methoxybenzenesulfonamide (Mtr),2,4,6-trimethoxybenzenesulfonamide (Mtb),2,6-dimethyl-4-methoxybenzenesulfonamide (Pme),2,3,5,6-tetramethyl-4-methoxybenzenesulfonamide (Mte),4-methoxybenzenesulfonamide (Mbs), 2,4,6-trimethylbenzenesulfonamide(Mts), 2,6-dimethoxy-4-methylbenzenesulfonamide (iMds),2,2,5,7,8-pentamethylchroman-6-sulfonamide (Pmc), methanesulfonamide(Ms), β-trimethylsilylethanesulfonamide (SES), 9-anthracenesulfonamide,4-(4′,8′-dimethoxynaphthylmethyl)benzenesulfonamide (DNMBS),benzylsulfonamide, trifluoromethylsulfonamide, and phenacylsulfonamide.Exemplary protecting groups are detailed herein, however, it will beappreciated that the present invention is not intended to be limited tothese protecting groups; rather, a variety of additional equivalentprotecting groups can be readily identified using the above criteria andutilized in the method of the present invention. Additionally, a varietyof protecting groups are described in Protecting Groups in OrganicSynthesis, T. W. Greene and P. G. M. Wuts, 3^(rd) edition, John Wiley &Sons, 1999, the entirety of which is incorporated herein by reference.

When substituents are described herein, the term “radical” or“optionally substituted radical” is sometimes used. In this context,“radical” means a moiety or functional group having an availableposition for attachment to the structure on which the substituent isbound. In general the point of attachment would bear a hydrogen atom ifthe substituent were an independent neutral molecule rather than asubstituent. The terms “radical” or “optionally-substituted radical” inthis context are thus interchangeable with “group” or“optionally-substituted group”.

As described herein, compounds of the invention may contain “optionallysubstituted” moieties. In general, the term “substituted”, whetherpreceded by the term “optionally” or not, means that one or morehydrogens of the designated moiety are replaced with a suitablesubstituent. Unless otherwise indicated, an “optionally substitutedgroup” or “optionally substituted radical” may have a suitablesubstituent at each substitutable position of the group, and when morethan one position in any given structure may be substituted with morethan one substituent selected from a specified group, the substituentmay be either the same or different at every position. Combinations ofsubstituents envisioned by this invention are preferably those thatresult in the formation of stable or chemically feasible compounds. Theterm “stable”, as used herein, refers to compounds that are notsubstantially altered when subjected to conditions to allow for theirproduction, detection, and, in certain embodiments, their recovery,purification, and use for one or more of the purposes disclosed herein.

In some chemical structures herein, substituents are shown attached to abond that crosses a bond in a ring of the depicted molecule. Thisconvention indicates that one or more of the substituents may beattached to the ring at any available position (usually in place of ahydrogen atom of the parent structure). In cases where an atom of a ringso substituted has two substitutable positions, two groups may bepresent on the same ring atom. Unless otherwise indicated, when morethan one substituent is present, each is defined independently of theothers, and each may have a different structure. In cases where thesubstituent shown crossing a bond of the ring is —R, this has the samemeaning as if the ring were said to be “optionally substituted” asdescribed in the preceding paragraph.

Suitable monovalent substituents on a substitutable carbon atom of an“optionally substituted” group are independently halogen;—(CH₂)₀₋₄R^(∘); —(CH₂)₀₋₄OR^(∘); —O—(CH₂)₀₋₄C(O)OR^(∘);—(CH₂)₀₋₄CH(OR^(∘))₂; —(CH₂)₀₋₄SR^(∘); —(CH₂)₀₋₄Ph, which may besubstituted with R^(∘); —(CH₂)₀₋₄O(CH₂)₀₋₁Ph which may be substitutedwith R^(∘); —CH═CHPh, which may be substituted with R^(∘); —NO₂; —CN;—N₃; —(CH₂)₀₋₄N(R^(∘))₂; —(CH₂)₀₋₄N(R^(∘))C(O)R^(∘); —N(R^(∘))C(S)R^(∘);—(CH₂)₀₋₄N(R^(∘))C(O)NR^(∘) ₂; —N(R^(∘))C(S)NR^(∘) ₂;—(CH₂)₀₋₄N(R^(∘))C(O)OR^(∘); —N(R^(∘))N(R^(∘))C(O)R^(∘);—N(R^(∘))N(R^(∘))C(O)NR^(∘) ₂; —N(R^(∘))N(R^(∘))C(O)OR^(∘);—(CH₂)₀₋₄C(O)R^(∘); —C(S)R^(∘); —(CH₂)₀₋₄C(O)OR^(∘);—(CH₂)₀₋₄C(O)N(R^(∘))₂; —(CH₂)₀₋₄C(O)SR^(∘); —(CH₂)₀₋₄C(O)OSiR^(∘) ₃;—(CH₂)₀₋₄OC(O)R^(∘); —OC(O)(CH₂)₀₋₄SR—, SC(S)SR^(∘);—(CH₂)₀₋₄SC(O)R^(∘); —(CH₂)₀₋₄C(O)NR^(∘) ₂; —C(S)NR^(∘) ₂; —C(S)SR^(∘);—SC(S)SR^(∘), —(CH₂)₀₋₄OC(O)NR^(∘) ₂; —C(O)N(OR^(∘))R^(∘);—C(O)C(O)R^(∘); —C(O)CH₂C(O)R^(∘); —C(NOR^(∘))R^(∘); —(CH₂)₀₋₄SSR^(∘);—(CH₂)₀₋₄S(O)₂R^(∘); —(CH₂)₀₋₄S(O)₂OR^(∘); —(CH₂)₀₋₄OS(O)₂R^(∘);—S(O)₂NR^(∘) ₂; —(CH₂)₀₋₄S(O)R^(∘); —N(R^(∘))S(O)₂NR^(∘) ₂;—N(R^(∘))S(O)₂R^(∘); —N(OR^(∘))R^(∘); —C(NH)NR^(∘) ₂; —P(O)₂R^(∘);—P(O)R^(∘) ₂; —OP(O)R^(∘) ₂; —OP(O)(OR^(∘))₂; SiR^(∘) ₃; —(C₁₋₄ straightor branched alkylene)O—N(R^(∘))₂; or —(C₁₋₄ straight or branchedalkylene)C(O)O—N(R^(∘))₂, wherein each R^(∘) may be substituted asdefined below and is independently hydrogen, C₁₋₈ aliphatic, —CH₂Ph,—O(CH₂)₀₋₁Ph, or a 5-6-membered saturated, partially unsaturated, oraryl ring having 0-4 heteroatoms independently selected from nitrogen,oxygen, or sulfur, or, notwithstanding the definition above, twoindependent occurrences of R^(∘), taken together with interveningatom(s), form a 3-12-membered saturated, partially unsaturated, or arylmono- or polycyclic ring having 0-4 heteroatoms independently selectedfrom nitrogen, oxygen, or sulfur, which may be substituted as definedbelow.

Suitable monovalent substituents on R^(∘) (or the ring formed by takingtwo independent occurrences of R^(∘) together with their interveningatoms), are independently halogen, —(CH₂)₀₋₂R^(•), -(haloR^(•)),—(CH₂)₀₋₂OH, —(CH₂)₀₋₂OR^(•), —(CH₂)₀₋₂CH(OR^(•))₂; —O(haloR^(•)), —CN,—N₃, —(CH₂)₀₋₂C(O)R^(•), —(CH₂)₀₋₂C(O)OH, —(CH₂)₀₋₂C(O)OR^(•),—(CH₂)₀₋₄C(O)N(R^(∘))₂; —(CH₂)₀₋₂SR^(•), —(CH₂)₀₋₂SH, —(CH₂)₀₋₂NH₂,—(CH₂)₀₋₂NHR^(•), —(CH₂)₀₋₂NR^(•) ₂, —NO₂, —SiR^(•) ₃, —OSiR^(•) ₃,—C(O)SR^(•), —(C₁₋₄ straight or branched alkylene)C(O)OR^(•), or—SSR^(•) wherein each R^(•) is unsubstituted or where preceded by “halo”is substituted only with one or more halogens, and is independentlyselected from C₁₋₄ aliphatic, —CH₂Ph, —O(CH₂)₀₋₁Ph, or a 5-6-memberedsaturated, partially unsaturated, or aryl ring having 0-4 heteroatomsindependently selected from nitrogen, oxygen, or sulfur. Suitabledivalent substituents on a saturated carbon atom of R^(∘) include ═O and═S.

Suitable divalent substituents on a saturated carbon atom of an“optionally substituted” group include the following: ═O, ═S, ═NNR*₂,═NNHC(O)R*, ═NNHC(O)OR*, ═NNHS(O)₂R*, ═NR*, ═NOR*, —O(C(R*₂))₂₋₃O—, or—S(C(R*₂))₂₋₃S—, wherein each independent occurrence of R* is selectedfrom hydrogen, C₁₋₆ aliphatic which may be substituted as defined below,or an unsubstituted 5-6-membered saturated, partially unsaturated, oraryl ring having 0-4 heteroatoms independently selected from nitrogen,oxygen, or sulfur. Suitable divalent substituents that are bound tovicinal substitutable carbons of an “optionally substituted” groupinclude: —O(CR*₂)₂₋₃O—, wherein each independent occurrence of R* isselected from hydrogen, C₁₋₆ aliphatic which may be substituted asdefined below, or an unsubstituted 5-6-membered saturated, partiallyunsaturated, or aryl ring having 0-4 heteroatoms independently selectedfrom nitrogen, oxygen, or sulfur.

Suitable substituents on the aliphatic group of R* include halogen,—R^(•), -(haloR^(•)), —OH, —OR^(•), —O(haloR^(•)), —CN, —C(O)OH,—C(O)OR^(•), —NH₂, —NHR^(•), —NR^(•) ₂, or —NO₂, wherein each R^(•) isunsubstituted or where preceded by “halo” is substituted only with oneor more halogens, and is independently C₁₋₄ aliphatic, —CH₂Ph,—O(CH₂)₀₋₁Ph, or a 5-6-membered saturated, partially unsaturated, oraryl ring having 0-4 heteroatoms independently selected from nitrogen,oxygen, or sulfur.

Suitable substituents on a substitutable nitrogen of an “optionallysubstituted” group include —R^(†), —NR^(†) ₂, —C(O)R^(†), —C(O)OR^(†),—C(O)C(O)R^(†), —C(O)CH₂C(O)R^(†), —S(O)₂R^(†), —S(O)₂NR^(†) ₂,—C(S)NR^(†) ₂, —C(NH)NR^(†) ₂, or —N(R^(†))S(O)₂R^(†); wherein eachR^(†) is independently hydrogen, C₁₋₆ aliphatic which may be substitutedas defined below, unsubstituted —OPh, or an unsubstituted 5-6-memberedsaturated, partially unsaturated, or aryl ring having 0-4 heteroatomsindependently selected from nitrogen, oxygen, or sulfur, or,notwithstanding the definition above, two independent occurrences ofR^(†), taken together with intervening atom(s) form an unsubstituted3-12-membered saturated, partially unsaturated, or aryl mono- orbicyclic ring having 0-4 heteroatoms independently selected fromnitrogen, oxygen, or sulfur. A substitutable nitrogen may be substitutedwith three R^(†) substituents to provide a charged ammonium moiety—N(R^(†))₃, wherein the ammonium moiety is further complexed with asuitable counterion.

Suitable substituents on the aliphatic group of R^(†) are independentlyhalogen, —R^(•), -(haloR^(•)), —OH, —OR^(•), —O(haloR^(•)), —CN,—C(O)OH, —C(O)OR^(•), —NH₂, —NHR^(•), —NR^(•) ₂, or —NO₂, wherein eachR^(•) is unsubstituted or where preceded by “halo” is substituted onlywith one or more halogens, and is independently C₁₋₄ aliphatic, —CH₂Ph,—O(CH₂)₀₋₁Ph, or a 5-6-membered saturated, partially unsaturated, oraryl ring having 0-4 heteroatoms independently selected from nitrogen,oxygen, or sulfur.

As used herein, the term “catalyst” refers to a substance the presenceof which increases the rate and/or extent of a chemical reaction, whilenot being consumed or undergoing a permanent chemical change itself.

As used herein, the term “multidentate” refers to ligands havingmultiple sites capable of coordinating to a single metal center.

As used herein, the term “activating moiety” refers to a moietycomprising one or more activating functional groups. In certainembodiments, an activating moiety improves the catalytic activity of ametal complex. In some embodiments, such improved catalytic activity ischaracterized by higher conversion of starting materials compared to ametal complex lacking an activating moiety. In some embodiments, suchimproved catalytic activity is characterized by higher rate ofconversion of starting materials compared to a metal complex lacking anactivating moiety. In some embodiments, such improved catalytic activityis characterized by higher yield of product compared to a metal complexlacking an activating moiety.

DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS

The present invention provides, among other things, unimolecular metalcomplexes for the copolymerization of carbon dioxide and epoxides andmethods of using the same. In certain embodiments, provided metalcomplexes contain a metal-ligand moiety tethered to one or moreactivating moieties. In some embodiments, an activating moiety comprisesa linker and one or more activating functional groups. In someembodiments, provided metal complexes act as polymerization catalysts.In certain embodiments, at least one activating functional group presenton the tethered moiety can act as a polymerization co-catalyst andthereby increase the rate of the copolymerization.

In certain embodiments, provided metal complexes include a metal atomcoordinated to a multidentate ligand and at least one activating moietytethered to the multidentate ligand. In certain embodiments, providedmetal complexes have the structure:

wherein:

-   -   M is a metal atom;

comprises a multidentate ligand;

-   -   (Z)_(m) represents one or more activating moieties attached to        the multidentate ligand, where        is a linker moiety covalently coupled to the ligand, each Z is        an activating functional group; and m is an integer from 1 to 4        representing the number of Z groups present on an individual        linker moiety.

In certain embodiments, provided metal complexes include a metal atomcoordinated to a multidentate ligand and at least one activating moietytethered to the multidentate ligand. In some embodiments, there are 1 to10 activating moieties

(Z)_(m) tethered to the multidentate ligand. In certain embodiments,there are 1 to 8 such activating moieties tethered to the multidentateligand. In certain embodiments, there are 1 to 4 such activatingmoieties tethered to the multidentate ligand.

I. Activating Functional Groups

In some embodiments, an activating functional group is selected from thegroup consisting of neutral nitrogen-containing functional groups,cationic moieties, phosphorous-containing functional groups, andcombinations of two or more of these.

I.a. Neutral Nitrogen-Containing Activating Groups

In some embodiments, one or more tethered activating functional groupson provided metal complexes are neutral nitrogen-containing moieties. Insome embodiments, such moieties include one or more of the structures inTable Z-1:

TABLE Z-1

or a combination of two or more of these,wherein:

-   -   each occurrence of R¹, and R² is independently hydrogen or an        optionally substituted radical selected from the group        consisting of C₁₋₂₀ aliphatic; C₁₋₂₀ heteroaliphatic; phenyl; a        3- to 8-membered saturated or partially unsaturated monocyclic        carbocycle, a 7-14 carbon saturated, partially unsaturated or        aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic        heteroaryl ring having 1-4 heteroatoms independently selected        from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated        or partially unsaturated heterocyclic ring having 1-3        heteroatoms independently selected from nitrogen, oxygen, or        sulfur; a 6- to 12-membered polycyclic saturated or partially        unsaturated heterocycle having 1-5 heteroatoms independently        selected from nitrogen, oxygen, or sulfur; or an 8- to        10-membered bicyclic heteroaryl ring having 1-5 heteroatoms        independently selected from nitrogen, oxygen, or sulfur; wherein        two or more R¹ and R² groups can be taken together with        intervening atoms to form one or more optionally substituted        rings optionally containing one or more additional heteroatoms;    -   each occurrence of R⁵ is independently hydrogen or an optionally        substituted radical selected from the group consisting of C₁₋₂₀        aliphatic; C₁₋₂₀ heteroaliphatic; phenyl; a 3- to 8-membered        saturated or partially unsaturated monocyclic carbocycle, a 7-14        carbon saturated, partially unsaturated or aromatic polycyclic        carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having        1-4 heteroatoms independently selected from nitrogen, oxygen, or        sulfur; a 3- to 8-membered saturated or partially unsaturated        heterocyclic ring having 1-3 heteroatoms independently selected        from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic        saturated or partially unsaturated heterocycle having 1-5        heteroatoms independently selected from nitrogen, oxygen, or        sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having        1-5 heteroatoms independently selected from nitrogen, oxygen, or        sulfur; wherein an R⁵ group can be taken with an R¹ or R² group        to form one or more optionally substituted rings;    -   each occurrence of R⁷ is independently hydrogen, a hydroxyl        protecting group, or an optionally substituted radical selected        from the group consisting of C₁₋₂₀ acyl; C₁₋₂₀ aliphatic; C₁₋₂₀        heteroaliphatic; phenyl; a 3- to 8-membered saturated or        partially unsaturated monocyclic carbocycle, a 7-14 carbon        saturated, partially unsaturated or aromatic polycyclic        carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having        1-4 heteroatoms independently selected from nitrogen, oxygen, or        sulfur; a 3- to 8-membered saturated or partially unsaturated        heterocyclic ring having 1-3 heteroatoms independently selected        from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic        saturated or partially unsaturated heterocycle having 1-5        heteroatoms independently selected from nitrogen, oxygen, or        sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having        1-5 heteroatoms independently selected from nitrogen, oxygen, or        sulfur;

In some embodiments, an activating functional group is an N-linked amino

group:

-   -   where R¹ and R² are as defined above.

In certain embodiments, R¹ and R² are both hydrogen. In someembodiments, only one of R¹ and R² is hydrogen. In certain embodiments,R¹ and R² are each independently an optionally substituted radicalselected from the group consisting of C₁₋₂₀ aliphatic; C₁₋₂₀heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, 8- to 10-memberedaryl and 3- to 7-membered heterocyclic. In certain embodiments, R¹ andR² are each independently an optionally substituted radical selectedfrom the group consisting of phenyl; a 3- to 8-membered saturated orpartially unsaturated monocyclic carbocycle, a 7-14 carbon saturated,partially unsaturated or aromatic polycyclic carbocycle; a 5- to6-membered monocyclic heteroaryl ring having 1-4 heteroatomsindependently selected from nitrogen, oxygen, or sulfur; a 3- to8-membered saturated or partially unsaturated heterocyclic ring having1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur;a 6- to 12-membered polycyclic saturated or partially unsaturatedheterocycle having 1-5 heteroatoms independently selected from nitrogen,oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ringhaving 1-5 heteroatoms independently selected from nitrogen, oxygen, orsulfur.

In certain embodiments, R¹ and R² are each independently an optionallysubstituted radical selected from the group consisting of C₁₋₁₂aliphatic and C₁₋₁₂ heteroaliphatic. In some embodiments, eachoccurrence of R¹ and R² is independently an optionally substituted C₁₋₂₀aliphatic. In some embodiments, R¹ and R² are each independentlyoptionally substituted C₁₋₁₂ aliphatic. In some embodiments, R¹ and R²are each independently optionally substituted C₁₋₆ aliphatic. In someembodiments, each occurrence of R¹ and R² is independently an optionallysubstituted C₁₋₂₀ heteroaliphatic. In some embodiments, each occurrenceof R¹ and R² is independently an optionally substituted C₁₋₁₂heteroaliphatic. In some embodiments, each occurrence of R¹ and R² isindependently an optionally substituted phenyl. In some embodiments,each occurrence of R¹ and R² is independently an optionally substituted8- to 10-membered aryl. In some embodiments, each occurrence of R¹ andR² is independently an optionally substituted phenyl group. In someembodiments, each occurrence of R¹ and R² is independently an optionallysubstituted 5- to 10-membered heteroaryl group. In some embodiments,each occurrence of R¹ and R² is independently an optionally substituted3- to 7-membered heterocyclic.

In certain embodiments, R¹ and R² are each independently hydrogen,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionallysubstituted phenyl, or optionally substituted benzyl. In certainembodiments, R¹ and R² are both methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R¹ and R²are each butyl. In some embodiments, R¹ and R² are each isopropyl. Insome embodiments, R¹ and R² are perfluoro. In some embodiments, R¹ andR² are —CF₂CF₃. In some embodiments, R¹ and R² are each phenyl. In someembodiments, R¹ and R² are each benzyl.

In some embodiments, R¹ and R² are taken together with intervening atomsto form one or more optionally substituted rings. In certainembodiments, R¹ and R² are taken together to form a ring fragmentselected from the group consisting of: —C(R^(y))₂—,—C(R^(y))₂C(R^(y))₂—, —C(R^(y))₂C(R^(y))₂C(R^(y))₂—,—C(R^(y))₂OC(R^(y))₂—, and —C(R^(y))₂NR^(y)C(R^(y))₂—. In certainembodiments, R¹ and R² are taken together to form a ring fragmentselected from the group consisting of: —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—,—CH₂OCH₂—, and —CH₂NR^(y)CH₂—. In some embodiments, R¹ and R² are takentogether to form an unsaturated linker moiety optionally containing oneor more additional heteroatoms. In some embodiments, the resultingnitrogen-containing ring is partially unsaturated. In certainembodiments, the resulting nitrogen-containing ring comprises a fusedpolycyclic heterocycle.

In specific embodiments, an N-linked amine activating functional groupis selected from the group consisting of:

In some embodiments, one or more activating functional groups is anN-linked

hydroxyl amine derivative:

-   -   wherein R¹ and R⁷ are as defined above.

In certain embodiments, R⁷ is hydrogen. In some embodiments, R⁷ is anoptionally substituted radical selected from the group consisting ofC₁₋₁₂ aliphatic, phenyl, 8- to 10-membered aryl, and 3- to 7-memberedheterocyclic. In certain embodiments, R⁷ is a C₁₋₁₂ aliphatic. Incertain embodiments, R⁷ is a C₁₋₆ aliphatic. In some embodiments, R⁷ isan optionally substituted 8- to 1-membered aryl group. In certainembodiments, R⁷ is an optionally substituted phenyl. In someembodiments, R⁷ is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, phenyl or benzyl.

In certain embodiments, R¹ is hydrogen. In some embodiments, R¹ is anoptionally substituted radical selected from the group consisting ofC₁₋₂₀ aliphatic; C₁₋₂₀ heteroaliphatic, 5- to 14-membered heteroaryl,phenyl, 8- to 10-membered aryl and 3- to 7-membered heterocyclic. Insome embodiments, R¹ is an optionally substituted radical selected fromthe group consisting of phenyl; a 3- to 8-membered saturated orpartially unsaturated monocyclic carbocycle, a 7-14 carbon saturated,partially unsaturated or aromatic polycyclic carbocycle; a 5- to6-membered monocyclic heteroaryl ring having 1-4 heteroatomsindependently selected from nitrogen, oxygen, or sulfur; a 3- to8-membered saturated or partially unsaturated heterocyclic ring having1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur;a 6- to 12-membered polycyclic saturated or partially unsaturatedheterocycle having 1-5 heteroatoms independently selected from nitrogen,oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ringhaving 1-5 heteroatoms independently selected from nitrogen, oxygen, orsulfur.

In some embodiments, R¹ is an optionally substituted radical selectedfrom the group consisting of C-1₂ aliphatic and C₁₋₁₂ heteroaliphatic.In some embodiments, R¹ is an optionally substituted C₁₋₂₀ aliphatic. Incertain embodiments, R¹ is an optionally substituted C₁₋₁₂ aliphatic. Insome embodiments, R¹ is an optionally substituted C₁₋₆ aliphatic. Insome embodiments, R¹ is an optionally substituted C₁₋₁₂ heteroaliphatic.In some embodiments, R¹ is an optionally substituted 8- to 10-memberedaryl. In certain embodiments, R¹ is an optionally substituted phenyl. Insome embodiments, R¹ is an optionally substituted 5- to 10-memberedheteroaryl. In some embodiments, R¹ is an optionally substituted 3- to7-membered heterocyclic.

In certain embodiments, R¹ is methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R¹ isbutyl. In some embodiments, R¹ is isopropyl. In some embodiments, R¹ isphenyl. In some embodiments, R¹ is benzyl. In some embodiments, R¹ isperfluoro. In some embodiments, R¹ is —CF₂CF₃. In certain embodiments,R¹ and R⁷ are taken together with intervening atoms to form one or moreoptionally substituted rings optionally containing one or moreadditional heteroatoms.

In certain embodiments, one or more N-linked hydroxyl amine activatingfunctional groups are selected from the group consisting of:

In some embodiments, an activating functional group in a provided metalcomplexis an amidine. In certain embodiments, such amidine activatingfunctional groups are selected from:

-   -   where each occurrence of R¹, R² and R⁵ are as defined above.

In certain embodiments, each R¹ and R² is hydrogen. In some embodiments,only one of R¹ and R² is hydrogen. In certain embodiments, each R¹ andR² is independently an optionally substituted radical selected from thegroup consisting of C₁₋₂₀ aliphatic; C₁₋₂₀ heteroaliphatic, 5- to14-membered heteroaryl, phenyl, 8- to 10-membered aryl and 3- to7-membered heterocyclic. In some embodiments, each R¹ and R² isindependently an optionally substituted radical selected from the groupconsisting of phenyl; a 3- to 8-membered saturated or partiallyunsaturated monocyclic carbocycle, a 7-14 carbon saturated, partiallyunsaturated or aromatic polycyclic carbocycle; a 5- to 6-memberedmonocyclic heteroaryl ring having 1-4 heteroatoms independently selectedfrom nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated orpartially unsaturated heterocyclic ring having 1-3 heteroatomsindependently selected from nitrogen, oxygen, or sulfur; a 6- to12-membered polycyclic saturated or partially unsaturated heterocyclehaving 1-5 heteroatoms independently selected from nitrogen, oxygen, orsulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5heteroatoms independently selected from nitrogen, oxygen, or sulfur.

In certain embodiments, R¹ and R² are each independently an optionallysubstituted radical selected from the group consisting of C₁₋₁₂aliphatic and C₁₋₁₂ heteroaliphatic. In some embodiments, eachoccurrence of R¹ and R² is independently an optionally substituted C₁₋₂₀aliphatic. In some embodiments, R¹ and R² are each independentlyoptionally substituted C₁₋₁₂ aliphatic. In some embodiments, R¹ and R²are each independently optionally substituted C₁₋₆ aliphatic. In someembodiments, each occurrence of R¹ and R² is independently an optionallysubstituted C₁₋₂₀ heteroaliphatic. In some embodiments, each occurrenceof R¹ and R² is independently an optionally substituted C₁₋₁₂heteroaliphatic. In some embodiments, each occurrence of R¹ and R² isindependently an optionally substituted 8- to 10-membered aryl. In someembodiments, each occurrence of R¹ and R² is independently an optionallysubstituted phenyl group. In some embodiments, each occurrence of R¹ andR² is independently an optionally substituted 5- to 10-memberedheteroaryl group. In some embodiments, each occurrence of R¹ and R² isindependently an optionally substituted 3- to 7-membered heterocyclic.

In certain embodiments, R¹ and R² are each independently hydrogen,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionallysubstituted phenyl, or optionally substituted benzyl. In certainembodiments, R¹ and R² are both methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R¹ and R²are each butyl. In some embodiments, R¹ and R² are each isopropyl. Insome embodiments, R¹ and R² are perfluoro. In some embodiments, R¹ andR² are —CF₂CF₃. In some embodiments, R¹ and R² are each phenyl. In someembodiments, R¹ and R² are each benzyl.

In some embodiments, R¹ and R² are taken together with intervening atomsto form one or more optionally substituted rings. In certainembodiments, R¹ and R² are taken together to form a ring fragmentselected from the group consisting of: —C(R^(y))₂—,—C(R^(y))₂C(R^(y))₂—, —C(R^(y))₂C(R^(y))₂C(R^(y))₂—,—C(R^(y))₂OC(R^(y))₂—, and —C(R^(y))₂NR^(y)C(R^(y))₂—. In certainembodiments, R¹ and R² are taken together to form a ring fragmentselected from the group consisting of: —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—,—CH₂OCH₂—, and —CH₂NR^(y)CH₂—. In some embodiments, R¹ and R² are takentogether to form an unsaturated linker moiety optionally containing oneor more additional heteroatoms. In some embodiments, the resultingnitrogen-containing ring is partially unsaturated. In certainembodiments, the resulting nitrogen-containing ring comprises a fusedpolycyclic heterocycle.

In certain embodiments, R⁵ is H. In certain embodiments, R⁵ isoptionally substituted C₁₋₂₀ aliphatic. In some embodiments, R⁵ isoptionally substituted 6- to 14-membered aryl. In certain embodiments,R⁵ is optionally substituted C₁₋₁₂ aliphatic. In some embodiments, R⁵ isoptionally substituted C₁₋₆ aliphatic. In certain embodiments, R⁵ isoptionally substituted phenyl.

In some embodiments, one or more R¹ or R² groups are taken together withR⁵ and intervening atoms to form an optionally substituted ring. Incertain embodiments, R¹ and R⁵ are taken together to form an optionallysubstituted 5- or 6-membered ring. In some embodiments, R² and R⁵ aretaken together to form an optionally substituted 5- or 6-membered ringoptionally containing one or more additional heteroatoms. In someembodiments, R¹, R² and R⁵ are taken together to form an optionallysubstituted fused ring system. In some embodiments such rings formed bycombinations of any of R¹, R² and R⁵ are partially unsaturated oraromatic.

In certain embodiments, an activating functional group is an N-linkedamidine:

In certain embodiments, N-linked amidine groups are selected from thegroup consisting of:

In certain embodiments, activating functional groups are amidinemoieties linked through the imine nitrogen:

In certain embodiments, imine-linked amidine activating functionalgroups are selected from the group consisting of:

In certain embodiments, activating functional groups are amidinemoieties linked through a carbon atom:

In certain embodiments, carbon-linked amidine activating groups areselected from the group consisting of:

In some embodiments, one or more activating functional groups is acarbamate. In certain embodiments, a carbamate is N-linked:

where R¹ and R² are as defined above. In some embodiments, a carbamateis O-linked:

where R¹ and R² are as defined above.

In certain embodiments, R¹ and R² are both hydrogen. In someembodiments, only one of R¹ and R² is hydrogen. In certain embodiments,R¹ and R² are each independently an optionally substituted radicalselected from the group consisting of C₁₋₂₀ aliphatic; C₁₋₂₀heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, 8- to 10-memberedaryl and 3- to 7-membered heterocyclic. In some embodiments, R¹ and R²are each independently an optionally substituted radical selected fromthe group consisting of phenyl; a 3- to 8-membered saturated orpartially unsaturated monocyclic carbocycle, a 7-14 carbon saturated,partially unsaturated or aromatic polycyclic carbocycle; a 5- to6-membered monocyclic heteroaryl ring having 1-4 heteroatomsindependently selected from nitrogen, oxygen, or sulfur; a 3- to8-membered saturated or partially unsaturated heterocyclic ring having1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur;a 6- to 12-membered polycyclic saturated or partially unsaturatedheterocycle having 1-5 heteroatoms independently selected from nitrogen,oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ringhaving 1-5 heteroatoms independently selected from nitrogen, oxygen, orsulfur.

In certain embodiments, R¹ and R² are each independently an optionallysubstituted radical selected from the group consisting of C₁₋₁₂aliphatic and C₁₋₁₂ heteroaliphatic. In some embodiments, eachoccurrence of R¹ and R² is independently an optionally substituted C₁₋₂₀aliphatic. In some embodiments, R¹ and R² are each independentlyoptionally substituted C₁₋₁₂ aliphatic. In some embodiments, R¹ and R²are each independently optionally substituted C₁₋₆ aliphatic. In someembodiments, each occurrence of R¹ and R² is independently an optionallysubstituted C₁₋₂₀ heteroaliphatic. In some embodiments, each occurrenceof R¹ and R² is independently an optionally substituted C₁₋₁₂heteroaliphatic. In some embodiments, each occurrence of R¹ and R² isindependently an optionally substituted 8- to 10-membered aryl. In someembodiments, each occurrence of R¹ and R² is independently an optionallysubstituted phenyl group. In some embodiments, each occurrence of R¹ andR² is independently an optionally substituted 5- to 10-memberedheteroaryl group. In some embodiments, each occurrence of R¹ and R² isindependently an optionally substituted 3- to 7-membered heterocyclic.

In certain embodiments, R¹ and R² are each independently hydrogen,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionallysubstituted phenyl, or optionally substituted benzyl. In certainembodiments, R¹ and R² are both methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R¹ and R²are each butyl. In some embodiments, R¹ and R² are each isopropyl. Insome embodiments, R¹ and R² are perfluoro. In some embodiments, R¹ andR² are —CF₂CF₃. In some embodiments, R¹ and R² are each phenyl. In someembodiments, R¹ and R² are each benzyl.

In some embodiments, R¹ and R² are taken together with intervening atomsto form one or more optionally substituted rings. In certainembodiments, R¹ and R² are taken together to form a ring fragmentselected from the group consisting of: —C(R^(y))₂—,—C(R^(y))₂C(R^(y))₂—, —C(R^(y))₂C(R^(y))₂C(R^(y))₂—,—C(R^(y))₂OC(R^(y))₂—, and —C(R^(y))₂NR^(y)C(R^(y))₂—. In certainembodiments, R¹ and R² are taken together to form a ring fragmentselected from the group consisting of: —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—,—CH₂OCH₂—, and —CH₂NR^(y)CH₂—. In some embodiments, R¹ and R² are takentogether to form an unsaturated linker moiety optionally containing oneor more additional heteroatoms. In some embodiments, the resultingnitrogen-containing ring is partially unsaturated. In certainembodiments, the resulting nitrogen-containing ring comprises a fusedpolycyclic heterocycle. In some embodiments, R² is selected from thegroup consisting of: methyl, t-butyl, t-amyl, benzyl, adamantyl, allyl,4-methoxycarbonylphenyl, 2-(methylsulfonyl)ethyl,2-(4-biphenylyl)-prop-2-yl, 2-(trimethylsilyl)ethyl, 2-bromoethyl, and9-fluorenylmethyl.

In some embodiments, an activating functional group is a guanidine orbis-guanidine group:

-   -   where each occurrence of R¹, R^(1′), R², R^(2′), R^(2″), R³, and        R^(3′) is independently hydrogen or an optionally substituted        radical selected from the group consisting of C₁₋₂₀ aliphatic;        C₁₋₂₀ heteroaliphatic; phenyl; a 3- to 8-membered saturated or        partially unsaturated monocyclic carbocycle, a 7-14 carbon        saturated, partially unsaturated or aromatic polycyclic        carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having        1-4 heteroatoms independently selected from nitrogen, oxygen, or        sulfur; a 3- to 8-membered saturated or partially unsaturated        heterocyclic ring having 1-3 heteroatoms independently selected        from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic        saturated or partially unsaturated heterocycle having 1-5        heteroatoms independently selected from nitrogen, oxygen, or        sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having        1-5 heteroatoms independently selected from nitrogen, oxygen, or        sulfur; wherein any two or more R¹, R^(1′), R², R^(2′), R^(2″),        R³, and R^(3′) groups can be taken together with intervening        atoms to form one or more optionally substituted rings        optionally containing one or more additional heteroatoms;

In certain embodiments, each occurrence of R¹, R^(1′), R², R^(2′),R^(2″), R³, and R^(3′) is hydrogen. In some embodiments, each occurrenceof R¹, R^(1′), R², R^(2′), R^(2″), R³, and R^(3′), is hydrogen or anoptionally substituted radical selected from the group consisting ofC₁₋₂₀ aliphatic; C₁₋₂₀ heteroaliphatic; 3- to 7-membered heterocyclic,phenyl, and 8- to 10-membered aryl. In some embodiments, each occurrenceof R¹, R^(1′), R², R^(2′), R^(2″), R³, and R^(3′) is hydrogen or anoptionally substituted radical selected from the group consisting ofphenyl; a 3- to 8-membered saturated or partially unsaturated monocycliccarbocycle, a 7-14 carbon saturated, partially unsaturated or aromaticpolycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ringhaving 1-4 heteroatoms independently selected from nitrogen, oxygen, orsulfur; a 3- to 8-membered saturated or partially unsaturatedheterocyclic ring having 1-3 heteroatoms independently selected fromnitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated orpartially unsaturated heterocycle having 1-5 heteroatoms independentlyselected from nitrogen, oxygen, or sulfur; or an 8- to 10-memberedbicyclic heteroaryl ring having 1-5 heteroatoms independently selectedfrom nitrogen, oxygen, or sulfur. In certain embodiments, eachoccurrence of R¹, R^(1′), R², R^(2′), R^(2″), R³, and R^(3′) isindependently hydrogen or an optionally substituted radical selectedfrom the group consisting of C₁₋₂₀ aliphatic, phenyl, and 8- to10-membered aryl. In certain embodiments, each occurrence of R¹ and R²is independently an optionally hydrogen or an optionally substitutedC₁₋₈ aliphatic, phenyl, or 8- to 10-membered aryl group. In someembodiments, each occurrence of R¹, R^(1′), R², R^(2′), R^(2″), R³, andR^(3′) is independently hydrogen or an optionally substituted C₁₋₂₀aliphatic. In some embodiments, each occurrence of R¹ and R² isindependently hydrogen an optionally substituted aryl group or anoptionally substituted C₁₋₈ aliphatic group. In some embodiments, eachoccurrence of R¹, R^(1′), R², R^(2′), R^(2″), R³, and R^(3′) isindependently hydrogen or an optionally substituted C₁₋₆ aliphaticgroup. In some embodiments, each occurrence of R¹, R^(1′), R², R^(2′),R^(2″), R³, and R^(3′) is independently hydrogen or an optionallysubstituted C₁₋₄ aliphatic group. In some embodiments, each occurrenceof R¹, R^(1′), R², R^(2′), R^(2″), R³, and R^(3′) is independently anoptionally substituted C₁₋₂₀ aliphatic. In some embodiments, R¹, R^(1′),R², R^(2′), R^(2″), R³, and R^(3′) are each independently optionallysubstituted C₁₋₁₂ aliphatic. In some embodiments, R¹, R^(1′), R²,R^(2′), R^(2″), R³, and R^(3′) are each independently optionallysubstituted C₁₋₆ aliphatic. In some embodiments, one or more occurrenceof R^(1′), R², R^(2′), R^(2″), R³, and R^(3′) is independently anoptionally substituted C₁₋₂₀ heteroaliphatic. In some embodiments, oneor more occurrence of R¹, R^(1′), R², R^(2′), R^(2″), R³, and R^(3′) isindependently hydrogen or an optionally substituted phenyl or 8- to10-membered aryl. In some embodiments, one or more occurrence of R¹,R^(1′), R², R^(2′), R^(2″), R³, and R^(3′) is independently hydrogen, oran optionally substituted 5- to 10-membered heteroaryl.

In some embodiments, R¹ is optionally substituted C₁₋₆ aliphatic. Incertain embodiments, R^(1′) is optionally substituted C₁₋₆ aliphatic. Incertain embodiments, R² is optionally substituted C₁₋₆ aliphatic. Incertain embodiments, R^(2′) is optionally substituted C₁₋₆ aliphatic. Incertain embodiments, R^(2″) is optionally substituted C₁₋₆ aliphatic. Incertain embodiments, R³ is optionally substituted C₁₋₆ aliphatic. Incertain embodiments, R^(3′) is optionally substituted C₁₋₆ aliphatic. Insome embodiments, each occurrence of R¹, R^(1′), R², R^(2′), R^(2″), R³,and R^(3′) is independently hydrogen, methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In certain embodiments,R¹, R^(1′), R², R^(2′), R^(2″), R³, and R^(3′) are each methyl or ethyl.In some embodiments, one or more R¹, R^(1′), R², R^(2′), R^(2″), R³, andR^(3′) is perfluoro.

In some embodiments, any two or more R¹, R^(1′), R², R^(2′), R^(2″), R³,and R^(3′) groups are taken together with intervening atoms to form oneor more optionally substituted rings.

In certain embodiments, R¹ and R² are taken together with interveningatoms to form an optionally substituted ring optionally containing oneor more additional heteroatoms. In some embodiments, R² and R^(2′) aretaken together with intervening atoms to form an optionally substitutedring optionally containing one or more additional heteroatoms. Incertain embodiments, R¹ and R³ are taken together with intervening atomsto form an optionally substituted ring optionally containing one or moreadditional heteroatoms. In some embodiments, [R² and R^(2′)] and [R¹ andR³] are taken together with intervening atoms to form an optionallysubstituted ring optionally containing one or more additionalheteroatoms. In some embodiments, three or more R¹, R^(1′), R², R^(2′),R^(2″), R³, and R^(3′) groups are taken together with any interveningatoms to form optionally substituted rings. In certain embodiments, R¹and R² groups are taken together to form an optionally substituted 5- or6-membered ring. In some embodiments, three or more R¹ and/or R²groupsare taken together to form an optionally substituted fused ring system.

In certain embodiments where an activating functional group is aguanidine or bis guanidine moiety, it is chosen from the groupconsisting of:

In some embodiments, an activating functional group is a urea:

where R¹, and R² are as defined above.

In certain embodiments, R¹ and R² are each hydrogen. In someembodiments, only one of R¹ and R² is hydrogen. In certain embodiments,R¹ and R² are each independently an optionally substituted radicalselected from the group consisting of C₁₋₂₀ aliphatic; C₁₋₂₀heteroaliphatic, phenyl; a 3- to 8-membered saturated or partiallyunsaturated monocyclic carbocycle, a 7-14 carbon saturated, partiallyunsaturated or aromatic polycyclic carbocycle; a 5- to 6-memberedmonocyclic heteroaryl ring having 1-4 heteroatoms independently selectedfrom nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated orpartially unsaturated heterocyclic ring having 1-3 heteroatomsindependently selected from nitrogen, oxygen, or sulfur; a 6- to12-membered polycyclic saturated or partially unsaturated heterocyclehaving 1-5 heteroatoms independently selected from nitrogen, oxygen, orsulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5heteroatoms independently selected from nitrogen, oxygen, or sulfur.

In certain embodiments, R¹ and R² are each independently an optionallysubstituted radical selected from the group consisting of C₁₋₁₂aliphatic and C₁₋₁₂ heteroaliphatic. In some embodiments, eachoccurrence of R¹ and R² is independently an optionally substituted C₁₋₂₀aliphatic. In some embodiments, R¹ and R² are each independentlyoptionally substituted C₁₋₁₂ aliphatic. In some embodiments, R¹ and R²are each independently optionally substituted C₁₋₆ aliphatic. In someembodiments, each occurrence of R¹ and R² is independently an optionallysubstituted C₁₋₂₀ heteroaliphatic. In some embodiments, each occurrenceof R¹ and R² is independently an optionally substituted C₁₋₁₂heteroaliphatic. In some embodiments, each occurrence of R¹ and R² isindependently an optionally substituted 8- to 10-membered aryl. In someembodiments, each occurrence of R¹ and R² is independently an optionallysubstituted phenyl group. In some embodiments, each occurrence of R¹ andR² is independently an optionally substituted 5- to 10-memberedheteroaryl group. In some embodiments, each occurrence of R¹ and R² isindependently an optionally substituted 3- to 7-membered heterocyclic.

In certain embodiments, R¹ and R² are each independently hydrogen,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionallysubstituted phenyl, or optionally substituted benzyl. In certainembodiments, R¹ and R² are both methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R¹ and R²are each butyl. In some embodiments, R¹ and R² are each isopropyl. Insome embodiments, R¹ and R² are perfluoro. In some embodiments, R¹ andR² are —CF₂CF₃. In some embodiments, R¹ and R² are each phenyl. In someembodiments, R¹ and R² are each benzyl.

In some embodiments, R¹ and R² are taken together with intervening atomsto form one or more optionally substituted rings. In certainembodiments, R¹ and R² are taken together to form a ring fragmentselected from the group consisting of: —C(R^(y))₂—,—C(R^(y))₂C(R^(y))₂—, —C(R^(y))₂C(R^(y))₂C(R^(y))₂—,—C(R^(y))₂OC(R^(y))₂—, and —C(R^(y))₂NR^(y)C(R^(y))₂—. In certainembodiments, R¹ and R² are taken together to form a ring fragmentselected from the group consisting of: —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—,—CH₂OCH₂—, and —CH₂NR^(y)CH₂—. In some embodiments, R¹ and R² are takentogether to form an unsaturated linker moiety optionally containing oneor more additional heteroatoms. In some embodiments, the resultingnitrogen-containing ring is partially unsaturated. In certainembodiments, the resulting nitrogen-containing ring comprises a fusedpolycyclic heterocycle.

In certain embodiments, activating functional groups are oxime orhydrazone groups:

-   -   where R¹, R², R⁵, and R⁷ are as defined above.

In certain embodiments, R¹ and R² are both hydrogen. In someembodiments, only one of R¹ and R² is hydrogen. In certain embodiments,R¹ and R² are each independently an optionally substituted radicalselected from the group consisting of C₁₋₂₀ aliphatic; C₁₋₂₀heteroaliphatic, 5- to 14-membered heteroaryl, 8- to 10-membered aryland 3- to 7-membered heterocyclic. In certain embodiments, R¹ and R² areeach independently an optionally substituted radical selected from thegroup consisting of phenyl; a 3- to 8-membered saturated or partiallyunsaturated monocyclic carbocycle, a 7-14 carbon saturated, partiallyunsaturated or aromatic polycyclic carbocycle; a 5- to 6-memberedmonocyclic heteroaryl ring having 1-4 heteroatoms independently selectedfrom nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated orpartially unsaturated heterocyclic ring having 1-3 heteroatomsindependently selected from nitrogen, oxygen, or sulfur; a 6- to12-membered polycyclic saturated or partially unsaturated heterocyclehaving 1-5 heteroatoms independently selected from nitrogen, oxygen, orsulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5heteroatoms independently selected from nitrogen, oxygen, or sulfur.

In certain embodiments, R¹ and R² are each independently an optionallysubstituted radical selected from the group consisting of C₁₋₁₂aliphatic and C₁₋₁₂ heteroaliphatic. In some embodiments, eachoccurrence of R¹ and R² is independently an optionally substituted C₁₋₂₀aliphatic. In some embodiments, R¹ and R² are each independentlyoptionally substituted C₁₋₁₂ aliphatic. In some embodiments, R¹ and R²are each independently optionally substituted C₁₋₆ aliphatic. In someembodiments, each occurrence of R¹ and R² is independently an optionallysubstituted C₁₋₂₀ heteroaliphatic. In some embodiments, each occurrenceof R¹ and R² is independently an optionally substituted C₁₋₁₂heteroaliphatic. In some embodiments, each occurrence of R¹ and R² isindependently an optionally substituted 8- to 10-membered aryl. In someembodiments, each occurrence of R¹ and R² is independently an optionallysubstituted phenyl group. In some embodiments, each occurrence of R¹ andR² is independently an optionally substituted 5- to 10-memberedheteroaryl group. In some embodiments, each occurrence of R¹ and R² isindependently an optionally substituted 3- to 7-membered heterocyclic.

In certain embodiments, R¹ and R² are each independently hydrogen,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionallysubstituted phenyl, or optionally substituted benzyl. In certainembodiments, R¹ and R² are both methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R¹ and R²are each butyl. In some embodiments, R¹ and R² are each isopropyl. Insome embodiments, R¹ and R² are perfluoro. In some embodiments, R¹ andR² are —CF₂CF₃. In some embodiments, R¹ and R² are each phenyl. In someembodiments, R¹ and R² are each benzyl.

In some embodiments, R¹ and R² are taken together with intervening atomsto form one or more optionally substituted rings. In certainembodiments, R¹ and R² are taken together to form a ring fragmentselected from the group consisting of: —C(R^(y))₂—,—C(R^(y))₂C(R^(y))₂—, —C(R^(y))₂C(R^(y))₂C(R^(y))₂—,—C(R^(y))₂OC(R^(y))₂—, and —C(R^(y))₂NR^(y)C(R^(y))₂—. In certainembodiments, R¹ and R² are taken together to form a ring fragmentselected from the group consisting of: —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—,—CH₂OCH₂—, and —CH₂NR^(y)CH₂—. In some embodiments, R¹ and R² are takentogether to form an unsaturated linker moiety optionally containing oneor more additional heteroatoms. In some embodiments, the resultingnitrogen-containing ring is partially unsaturated. In certainembodiments, the resulting nitrogen-containing ring comprises a fusedpolycyclic heterocycle.

In certain embodiments, R⁵ is H. In certain embodiments, R⁵ isoptionally substituted C₁₋₂₀ aliphatic, and in some embodiments R⁵ isoptionally substituted 6- to 14-membered aryl. In certain embodiments,R⁵ is optionally substituted C₁₋₁₂ aliphatic and in some embodiments,optionally substituted C₁₋₆ aliphatic. In certain embodiments, R⁵ isoptionally substituted phenyl.

In some embodiments, one or more R¹ or R² groups are taken together withR⁵ and intervening atoms to form an optionally substituted ring. Incertain embodiments, R¹ and R⁵ are taken together to form an optionallysubstituted 5- or 6-membered ring. In some embodiments, R² and R⁵ aretaken together to form an optionally substituted 5- or 6-membered ringoptionally containing one or more additional heteroatoms. In someembodiments, R¹, R² and R⁵ are taken together to form an optionallysubstituted fused ring system. In some embodiments such rings formed bycombinations of any of R¹, R² and R⁵ are partially unsaturated oraromatic.

In certain embodiments, R⁷ is —H. In certain embodiments, R⁷ isoptionally substituted C₁₋₂₀ aliphatic, while in some embodiments R⁵ isoptionally substituted 6- to 14-membered aryl. In certain embodiments,R⁷ is optionally substituted C₁₋₁₂ aliphatic or in some embodiments,optionally substituted C₁₋₆ aliphatic. In certain embodiments, R⁷ isoptionally substituted C₁₋₁₂ acyl or in some embodiments, optionallysubstituted C₁₋₆ acyl. In certain embodiments, R⁷ is optionallysubstituted phenyl. In some embodiments, R⁷ is a hydroxyl protectinggroup. In some embodiments, R⁷ is a silyl protecting group.

In some embodiments, an activating functional group is an N-oxidederivative:

where R¹ and R² are as defined above.

In certain embodiments, R¹ and R² are both hydrogen. In someembodiments, only one of R¹ and R² is hydrogen. In certain embodiments,R¹ and R² are each independently an optionally substituted radicalselected from the group consisting of C₁₋₂₀ aliphatic; C₁₋₂₀heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, or 8- to10-membered aryl and 3- to 7-membered heterocyclic.

In certain embodiments, R¹ and R² are each independently an optionallysubstituted radical selected from the group consisting of C₁₋₁₂aliphatic and C₁₋₁₂ heteroaliphatic. In some embodiments, eachoccurrence of R¹ and R² is independently an optionally substituted C₁₋₂₀aliphatic. In some embodiments, R¹ and R² are each independentlyoptionally substituted C₁₋₁₂ aliphatic. In some embodiments, R¹ and R²are each independently optionally substituted C₁₋₆ aliphatic. In someembodiments, each occurrence of R¹ and R² is independently an optionallysubstituted C₁₋₂₀ heteroaliphatic. In some embodiments, each occurrenceof R¹ and R² is independently an optionally substituted C₁₋₁₂heteroaliphatic. In some embodiments, each occurrence of R¹ and R² isindependently an optionally substituted 8- to 10-membered aryl. In someembodiments, each occurrence of R¹ and R² is independently an optionallysubstituted phenyl group. In some embodiments, each occurrence of R¹ andR² is independently an optionally substituted 5- to 10-memberedheteroaryl group. In some embodiments, each occurrence of R¹ and R² isindependently an optionally substituted 3- to 7-membered heterocyclic.

In certain embodiments, R¹ and R² are each independently hydrogen,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionallysubstituted phenyl, or optionally substituted benzyl. In certainembodiments, R¹ and R² are both methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R and R²are each butyl. In some embodiments, R¹ and R² are each isopropyl. Insome embodiments, R¹ and R² are perfluoro. In some embodiments, R¹ andR² are —CF₂CF₃. In some embodiments, R¹ and R² are each phenyl. In someembodiments, R¹ and R² are each benzyl.

In some embodiments, R¹ and R² are taken together with intervening atomsto form one or more optionally substituted rings. In certainembodiments, R¹ and R² are taken together to form a ring fragmentselected from the group consisting of: —C(R^(y))₂—,—C(R^(y))₂C(R^(y))₂—, —C(R^(y))₂C(R^(y))₂C(R^(y))₂—,—C(R^(y))₂OC(R^(y))₂—, and —C(R^(y))₂NR^(y)C(R^(y))₂—. In certainembodiments, R¹ and R² are taken together to form a ring fragmentselected from the group consisting of: —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—,—CH₂OCH₂—, and —CH₂NR^(y)CH₂—. In some embodiments, R¹ and R² are takentogether to form an unsaturated linker moiety optionally containing oneor more additional heteroatoms. In some embodiments, the resultingnitrogen-containing ring is partially unsaturated. In certainembodiments, the resulting nitrogen-containing ring comprises a fusedpolycyclic heterocycle.

In specific embodiments, an N-oxide activating functional group isselected from the group consisting of:

I.b. Cationic Activating Groups

In some embodiments, one or more tethered activating functional groupson provided metal complexes are cationic moieties include cationicmoieties. In some embodiments, such moieties include one or more of thestructures in Table Z-2:

TABLE Z-2

or a combination of two or more of these,wherein:

-   -   each occurrence of R¹, R², and R³ is as previously defined;    -   R^(4′) is hydrogen, hydroxyl, optionally substituted C₁₋₂₀        aliphatic;    -   each occurrence of R⁵ and R⁶ is independently hydrogen or an        optionally substituted radical selected from the group        consisting of C₁₋₂₀ aliphatic; C₁₋₂₀ heteroaliphatic; phenyl; a        3- to 8-membered saturated or partially unsaturated monocyclic        carbocycle, a 7-14 carbon saturated, partially unsaturated or        aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic        heteroaryl ring having 1-4 heteroatoms independently selected        from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated        or partially unsaturated heterocyclic ring having 1-3        heteroatoms independently selected from nitrogen, oxygen, or        sulfur; a 6- to 12-membered polycyclic saturated or partially        unsaturated heterocycle having 1-5 heteroatoms independently        selected from nitrogen, oxygen, or sulfur; or an 8- to        10-membered bicyclic heteroaryl ring having 1-5 heteroatoms        independently selected from nitrogen, oxygen, or sulfur; wherein        R⁵ and R⁶ can be taken together with intervening atoms to form        one or more optionally substituted rings optionally containing        one or more heteroatoms, and an R⁵ or R⁶ group can be taken with        an R¹ or R² group to form one or more optionally substituted        rings;    -   each occurrence of R⁸, R⁹, and R¹⁰ is independently hydrogen or        an optionally substituted radical selected from the group        consisting of C₁₋₂₀ aliphatic; C₁₋₂₀ heteroaliphatic; phenyl; a        3- to 8-membered saturated or partially unsaturated monocyclic        carbocycle, a 7-14 carbon saturated, partially unsaturated or        aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic        heteroaryl ring having 1-4 heteroatoms independently selected        from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated        or partially unsaturated heterocyclic ring having 1-3        heteroatoms independently selected from nitrogen, oxygen, or        sulfur; a 6- to 12-membered polycyclic saturated or partially        unsaturated heterocycle having 1-5 heteroatoms independently        selected from nitrogen, oxygen, or sulfur; or an 8- to        10-membered bicyclic heteroaryl ring having 1-5 heteroatoms        independently selected from nitrogen, oxygen, or sulfur; wherein        any two or more R⁸, R⁹ and R¹⁰ groups can be taken together with        intervening atoms to form one or more optionally substituted        rings;    -   each occurrence of R¹¹ is independently selected from the group        consisting of: halogen, —NO₂, —CN, —SR^(y), —S(O)R^(y),        —S(O)₂R^(y), —NR^(y)C(O)R^(y), —OC(O)R^(y), —CO₂R^(y), —NCO,        —N₃, —OR⁷, —OC(O)N(R^(y))₂, —N(R^(y))₂, —NR^(y)C(O)R^(y),        —NR^(y)C(O)OR^(y); or an optionally substituted radical selected        from the group consisting of C₁₋₂₀ aliphatic; C₁₋₂₀        heteroaliphatic; phenyl; a 3- to 8-membered saturated or        partially unsaturated monocyclic carbocycle, a 7-14 carbon        saturated, partially unsaturated or aromatic polycyclic        carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having        1-4 heteroatoms independently selected from nitrogen, oxygen, or        sulfur; a 3- to 8-membered saturated or partially unsaturated        heterocyclic ring having 1-3 heteroatoms independently selected        from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic        saturated or partially unsaturated heterocycle having 1-5        heteroatoms independently selected from nitrogen, oxygen, or        sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having        1-5 heteroatoms independently selected from nitrogen, oxygen, or        sulfur, where each occurrence of R^(y) is independently hydrogen        or an optionally substituted C₁₋₆ aliphatic group, and where two        or more adjacent R¹¹ groups can be taken together to form an        optionally substituted saturated, partially unsaturated, or        aromatic 5- to 12-membered ring containing 0 to 4 heteroatoms;    -   X⁻ is any anion, and    -   Ring A is an optionally substituted, 5- to 10-membered        heteroaryl group.

In certain embodiments, a cationic activating functional group is aprotonated amine:

where R¹ and R² are as defined above.

In certain embodiments, R¹ and R² are both hydrogen. In someembodiments, only one of R¹ and R² is hydrogen. In certain embodiments,R¹ and R² are each independently an optionally substituted radicalselected from the group consisting of C₁₋₂₀ aliphatic; C₁₋₂₀heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, or 8- to10-membered aryl and 3- to 7-membered heterocyclic. In certainembodiments, R¹ and R² are each independently an optionally substitutedradical selected from the group consisting of phenyl; a 3- to 8-memberedsaturated or partially unsaturated monocyclic carbocycle, a 7-14 carbonsaturated, partially unsaturated or aromatic polycyclic carbocycle; a 5-to 6-membered monocyclic heteroaryl ring having 1-4 heteroatomsindependently selected from nitrogen, oxygen, or sulfur; a 3- to8-membered saturated or partially unsaturated heterocyclic ring having1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur;a 6- to 12-membered polycyclic saturated or partially unsaturatedheterocycle having 1-5 heteroatoms independently selected from nitrogen,oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ringhaving 1-5 heteroatoms independently selected from nitrogen, oxygen, orsulfur.

In certain embodiments, R¹ and R² are each independently an optionallysubstituted radical selected from the group consisting of C₁₋₁₂aliphatic and C₁₋₁₂ heteroaliphatic. In some embodiments, eachoccurrence of R¹ and R² is independently an optionally substituted C₁₋₂₀aliphatic. In some embodiments, R¹ and R² are each independentlyoptionally substituted C₁₋₁₂ aliphatic. In some embodiments, R¹ and R²are each independently optionally substituted C₁₋₆ aliphatic. In someembodiments, each occurrence of R¹ and R² is independently an optionallysubstituted C₁ 2₀ heteroaliphatic. In some embodiments, each occurrenceof R¹ and R² is independently an optionally substituted C₁₋₁₂heteroaliphatic. In some embodiments, each occurrence of R¹ and R² isindependently an optionally substituted 8- to 10-membered aryl. In someembodiments, each occurrence of R¹ and R² is independently an optionallysubstituted phenyl group. In some embodiments, each occurrence of R¹ andR² is independently an optionally substituted 5- to 10-memberedheteroaryl group. In some embodiments, each occurrence of R¹ and R² isindependently an optionally substituted 3- to 7-membered heterocyclic.

In certain embodiments, R¹ and R² are each independently hydrogen,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionallysubstituted phenyl, or optionally substituted benzyl. In certainembodiments, R¹ and R² are both methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R¹ and R²are each butyl. In some embodiments, R¹ and R² are each isopropyl. Insome embodiments, R¹ and R² are perfluoro. In some embodiments, R¹ andR² are —CF₂CF₃. In some embodiments, R¹ and R² are each phenyl. In someembodiments, R¹ and R² are each benzyl.

In some embodiments, R¹ and R² are taken together with intervening atomsto form one or more optionally substituted rings. In certainembodiments, R¹ and R² are taken together to form a ring fragmentselected from the group consisting of: —C(R^(y))₂—, —C(R′)₂C(R^(y))₂—,—C(R^(y))₂C(R^(y))₂C(R^(y))₂—, —C(R^(y))₂OC(R^(y))₂—, and—C(R′)₂NR^(y)C(R^(y))₂—. In certain embodiments, R¹ and R² are takentogether to form a ring fragment selected from the group consisting of:—CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—, —CH₂OCH₂—, and —CH₂NR^(y)CH₂—. In someembodiments, R¹ and R² are taken together to form an unsaturated linkermoiety optionally containing one or more additional heteroatoms. In someembodiments, the resulting nitrogen-containing ring is partiallyunsaturated. In certain embodiments, the resulting nitrogen-containingring comprises a fused polycyclic heterocycle.

In specific embodiments, a protonated amine activating functional groupis selected from the group consisting of:

In certain embodiments, an activating functional group is a guanidiniumgroup:

In some embodiments, each of R⁴, R⁵, R⁶, R⁷, and R⁸ is hydrogen. In someembodiments, each occurrence of R⁴, R⁵, R⁶, R⁷, and R⁸ is independentlyhydrogen or C₁₋₂₀ aliphatic. In some embodiments, each occurrence of R⁴,R⁵, R⁶, R⁷, and R⁸ is independently hydrogen or C₁₋₁₂ aliphatic. In someembodiments, each occurrence of R⁴, R⁵, R⁶, R⁷, and R⁸ is independentlyhydrogen or C₁₋₂₀ heteroaliphatic. In some embodiments, each occurrenceof R⁴, R⁵, R⁶, R⁷, and R⁸ is independently hydrogen or phenyl. In someembodiments, each occurrence of R⁴, R⁵, R⁶, R⁷, and R⁸ is independentlyhydrogen or 8- to 10-membered aryl. In some embodiments, each occurrenceof R⁴, R⁵, R⁶, R⁷, and R⁸ is independently hydrogen or 5- to 10-memberedheteroaryl. In some embodiments, each occurrence of R⁴, R⁵, R⁶, R⁷, andR⁸ is independently hydrogen or 3- to 7-membered heterocyclic. In someembodiments, one or more of R⁴, R⁵, R⁶, and R⁷ is optionally substitutedC₁₋₁₂ aliphatic. In certain embodiments, any of (R⁴ and R⁵), (R⁵ andR⁶), (R⁶ and R⁷), (R⁷ and R⁸), and (R⁴ and R⁷) can be taken togetherwith intervening atoms to form one or more optionally substituted rings.In some embodiments, (R⁴ and R⁵) and (R⁶ and R⁷) are taken together toform rings.

It will be appreciated that when a guanidinium cation is depicted as

all such resonance forms are contemplated and encompassed by the presentdisclosure. For example, such groups can also be depicted as

In specific embodiments, a guanidinium activating functional group isselected from the group consisting of:

In some embodiments, an activating functional group is a sulfonium groupor an arsonium group:

where R⁸, R⁹, and R¹⁰ are as defined above.

In certain embodiments, each occurrence of R⁸, R⁹, and R¹⁰ isindependently optionally substituted C₁₋₂₀ aliphatic. In someembodiments, each occurrence of R⁸, R⁹, and R¹⁰ is independentlyhydrogen or optionally substituted C₁₋₂₀ heteroaliphatic. In someembodiments, each occurrence of R⁹, R¹⁰, and R¹¹ is independentlyhydrogen or optionally substituted phenyl. In some embodiments, eachoccurrence of R⁹, R¹⁰, and R¹¹ is independently hydrogen or optionallysubstituted 8- to 10-membered aryl. In some embodiments, each occurrenceof R⁸, R⁹, and R¹⁰ is independently hydrogen or optionally substituted5- to 10-membered heteroaryl. In some embodiments, each occurrence ofR⁹, R¹⁰, and R¹¹ is independently hydrogen or optionally substituted 3-to 7-membered heterocyclic. In some embodiments, R⁸ and R⁹ are takentogether with intervening atoms to form one or more rings selected fromthe group consisting of: optionally substituted C₃₋C₁₄ carbocycle,optionally substituted 3- to 14-membered heterocycle, optionallysubstituted C₆₋C₁₀ aryl, and optionally substituted 5- to 10-memberedheteroaryl.

In certain embodiments, R⁸, R⁹ and R¹⁰ are each methyl. In certainembodiments, R⁸, R⁹ and R¹⁰ are each phenyl.

In specific embodiments, an arsonium activating functional group isselected from the group consisting of:

In some embodiments, an activating functional group is an optionallysubstituted nitrogen-containing heterocycle. In certain embodiments, thenitrogen-containing heterocycle is an aromatic heterocycle. In certainembodiments, the optionally substituted nitrogen-containing heterocycleis selected from the group consisting of: pyridine, imidazole,pyrrolidine, pyrazole, quinoline, thiazole, dithiazole, oxazole,triazole, pyrazolem, isoxazole, isothiazole, tetrazole, pyrazine,thiazine, and triazine.

In some embodiments, a nitrogen-containing heterocycle includes aquaternarized nitrogen atom. In certain embodiments, anitrogen-containing heterocycle includes an iminium moiety such as

In certain embodiments, the optionally substituted nitrogen-containingheterocycle is selected from the group consisting of pyridinium,imidazolium, pyrrolidinium, pyrazolium, quinolinium, thiazolium,dithiazolium, oxazolium, triazolium, isoxazolium, isothiazolium,tetrazolium, pyrazinium, thiazinium, and triazinium.

In certain embodiments, a nitrogen-containing heterocycle is linked to ametal complex via a ring nitrogen atom. In some embodiments, a ringnitrogen to which the attachment is made is thereby quaternized, and insome embodiments, linkage to a metal complex takes the place of an N—Hbond and the nitrogen atom thereby remains neutral. In certainembodiments, an optionally substituted N-linked nitrogen-containingheterocycle is a pyridinium derivative. In certain embodiments,optionally substituted N-linked nitrogen-containing heterocycle is animidazolium derivative. In certain embodiments, optionally substitutedN-linked nitrogen-containing heterocycle is a thiazolium derivative. Incertain embodiments, optionally substituted N-linked nitrogen-containingheterocycle is a pyridinium derivative.

In some embodiments, an activating functional group is

In certain embodiments, ring A is an optionally substituted, 5- to10-membered heteroaryl group. In some embodiments, Ring A is anoptionally substituted, 6-membered heteroaryl group. In someembodiments, Ring A is a ring of a fused heterocycle. In someembodiments, Ring A is an optionally substituted pyridyl group.

In some embodiments, R¹² is hydrogen. In some embodiments, R¹² is anoptionally substituted C₁₋₂₀ aliphatic group. In some embodiments, R¹²is C₁₋₂₀ heteroaliphatic. In some embodiments, R¹² is optionallysubstituted phenyl, 8- to 10-membered aryl; 5- to 10-memberedheteroaryl. In some embodiments, R¹² is 3- to 7-membered heterocyclic.In some embodiments, R¹² is an optionally substituted C₁₋₁₂ aliphaticgroup. In some embodiments, R¹² is neopentyl. In some embodiments, R¹²is oxide or hydroxyl.

In some embodiments, when Z is

ring A is other than an imidazole, an oxazole, or a thiazole.

In specific embodiments, a nitrogen-containing heterocycle activatingfunctional group is selected from the group consisting of:

In some embodiments, an activating functional group is

where R¹, R² and R⁵ are as defined above.

In certain embodiments, R¹ and R² are each hydrogen. In someembodiments, only one of R¹ and R² is hydrogen. In certain embodiments,R¹ and R² are each independently an optionally substituted radicalselected from the group consisting of C₁₋₂₀ aliphatic; C₁₋₂₀heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, 8- to 10-memberedaryl and 3- to 7-membered heterocyclic. In certain embodiments, R¹ andR² are each independently an optionally substituted radical selectedfrom the group consisting of phenyl; a 3- to 8-membered saturated orpartially unsaturated monocyclic carbocycle, a 7-14 carbon saturated,partially unsaturated or aromatic polycyclic carbocycle; a 5- to6-membered monocyclic heteroaryl ring having 1-4 heteroatomsindependently selected from nitrogen, oxygen, or sulfur; a 3- to8-membered saturated or partially unsaturated heterocyclic ring having1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur;a 6- to 12-membered polycyclic saturated or partially unsaturatedheterocycle having 1-5 heteroatoms independently selected from nitrogen,oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ringhaving 1-5 heteroatoms independently selected from nitrogen, oxygen, orsulfur.

In certain embodiments, R¹ and R² are each independently an optionallysubstituted radical selected from the group consisting of C₁₋₁₂aliphatic and C₁₋₁₂ heteroaliphatic. In some embodiments, eachoccurrence of R¹ and R² is independently an optionally substituted C₁₋₂₀aliphatic. In some embodiments, R¹ and R² are each independentlyoptionally substituted C₁₋₁₂ aliphatic. In some embodiments, R¹ and R²are each independently optionally substituted C₁₋₆ aliphatic. In someembodiments, each occurrence of R¹ and R² is independently an optionallysubstituted C₁₋₂₀ heteroaliphatic. In some embodiments, each occurrenceof R¹ and R² is independently an optionally substituted C₁₋₁₂heteroaliphatic. In some embodiments, each occurrence of R¹ and R² isindependently an optionally substituted 8- to 10-membered aryl. In someembodiments, each occurrence of R¹ and R² is independently an optionallysubstituted phenyl group. In some embodiments, each occurrence of R¹ andR² is independently an optionally substituted 5- to 10-memberedheteroaryl group. In some embodiments, each occurrence of R¹ and R² isindependently an optionally substituted 3- to 7-membered heterocyclic.

In certain embodiments, R¹ and R² are each independently hydrogen,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionallysubstituted phenyl, or optionally substituted benzyl. In certainembodiments, R¹ and R² are both methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R¹ and R²are each butyl. In some embodiments, R¹ and R² are each isopropyl. Insome embodiments, R¹ and R² are perfluoro. In some embodiments, R¹ andR² are —CF₂CF₃. In some embodiments, R¹ and R² are each phenyl. In someembodiments, R¹ and R² are each benzyl.

In some embodiments, R¹ and R² are taken together with intervening atomsto form one or more optionally substituted rings. In certainembodiments, R¹ and R² are taken together to form a ring fragmentselected from the group consisting of: —C(R^(y))₂—,—C(R^(y))₂C(R^(y))₂—, —C(R^(y))₂C(R^(y))₂C(R^(y))₂—,—C(R^(y))₂OC(R^(y))₂—, and —C(R^(y))₂NR^(y)C(R^(y))₂—. In certainembodiments, R¹ and R² are taken together to form a ring fragmentselected from the group consisting of: —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—,—CH₂OCH₂—, and —CH₂NR^(y)CH₂—. In some embodiments, R¹ and R² are takentogether to form an unsaturated linker moiety optionally containing oneor more additional heteroatoms. In some embodiments, the resultingnitrogen-containing ring is partially unsaturated. In certainembodiments, the resulting nitrogen-containing ring comprises a fusedpolycyclic heterocycle.

In certain embodiments, R⁵ is H. In certain embodiments, R⁵ isoptionally substituted C₁₋₂₀ aliphatic, and in some embodiments R⁵ isoptionally substituted 6- to 14-membered aryl. In certain embodiments,R⁵ is optionally substituted C₁₋₁₂ aliphatic and in some embodiments,optionally substituted C₁₋₆ aliphatic. In certain embodiments, R⁵ ismethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl orbenzyl. In some embodiments, R⁵ is perfluoro. In some embodiments, R⁵is-CF₂CF₃. In certain embodiments, R⁵ is optionally substituted phenyl.

In some embodiments, one or more R¹ or R² groups are taken together withR⁵ and intervening atoms to form an optionally substituted ring. Incertain embodiments, R¹ and R⁵ are taken together to form an optionallysubstituted 5- or 6-membered ring. In some embodiments, R² and R⁵ aretaken together to form an optionally substituted 5- or 6-membered ringoptionally containing one or more additional heteroatoms. In someembodiments, R¹, R² and R⁵ are taken together to form an optionallysubstituted fused ring system. In some embodiments such rings formed bycombinations of any of R¹, R² and R⁵ are partially unsaturated oraromatic.

In some embodiments, an activating functional group is

where R¹ and R² are as defined above.

In certain embodiments, R¹ and R² are each independently an optionallysubstituted group selected from the group consisting of C₁₋₂₀ aliphatic;C₁₋₂₀ heteroaliphatic; phenyl; and 8-10-membered aryl. In someembodiments, R¹ and R² are each independently an optionally substituted4-7-membered heterocyclic. In some embodiments, R¹ and R² can be takentogether with intervening atoms to form one or more rings selected fromthe group consisting of: optionally substituted C₃-C₁₄ carbocycle,optionally substituted C₃-C₁₄ heterocycle, optionally substituted C₆-C₁₀aryl, and optionally substituted 5- to 10-membered heteroaryl. In someembodiments, R¹ and R² are each independently selected from the groupconsisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, or benzyl. In some embodiments, each occurrence of R¹ and R² isindependently perfluoro. In some embodiments, each occurrence of R¹ andR² is independently —CF₂CF₃.

In some embodiments, an activating functional group is

where R¹, R², R³, and R⁵ are as defined above.

In certain embodiments, R¹, R², and R³ are each independently anoptionally substituted group selected from the group consisting of C₁₋₂₀aliphatic; C₁₋₂₀ heteroaliphatic; phenyl; and 8-10-membered aryl. Incertain embodiments, R¹, R², and R³ are each independently an optionallysubstituted 4-7-membered heterocyclic. In some embodiments, R¹ and R²can be taken together with intervening atoms to form one or more ringsselected from the group consisting of: optionally substituted C₃-C₁₄carbocycle, optionally substituted C₃-C₁₄ heterocycle, optionallysubstituted C₆-C₁₀ aryl, and optionally substituted 5- to 10-memberedheteroaryl. In certain embodiments, R¹, R², and R³ are eachindependently an optionally substituted C₁₋₆ aliphatic. In certainembodiments, R¹, R², and R³ are each independently selected from thegroup consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, or benzyl. In certain embodiments, R¹, R², and R³ are eachindependently perfluoro. In some embodiments, R¹, R², and R³ are eachindependently —CF₂CF₃.

In certain embodiments, R⁵ is hydrogen. In certain embodiments R⁵ is anoptionally substituted group selected from the group consisting of C₁₋₁₂aliphatic and C₁₋₁₂ heteroaliphatic. In some embodiments, R⁵ is anoptionally substituted C₁₋₁₂ aliphatic. In some embodiments, R⁵ isoptionally substituted C₁₋₆ aliphatic.

In some embodiments, an activating functional group is

In certain embodiments, R¹ and R² are each independently an optionallysubstituted group selected from the group consisting of C₁₋₂₀ aliphatic;C₁₋₂₀ heteroaliphatic; phenyl; and 8-10-membered aryl. In someembodiments, R¹ and R² are each independently an optionally substituted4-7-membered heterocyclic. In some embodiments, R¹ and R² can be takentogether with intervening atoms to form one or more rings selected fromthe group consisting of: optionally substituted C₃-C₁₄ carbocycle,optionally substituted C₃-C₁₄ heterocycle, optionally substituted C₆-C₁₀aryl, and optionally substituted 5- to 10-membered heteroaryl. In someembodiments, R¹ and R² are each independently selected from the groupconsisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, or benzyl. In some embodiments, each occurrence of R¹ and R² isindependently perfluoro. In some embodiments, each occurrence of R¹ andR² is independently —CF₂CF₃.

In certain embodiments, R⁵ and R⁶ are each independently an optionallysubstituted group selected from the group consisting of C₁₋₂₀ aliphatic;C₁₋₂₀ heteroaliphatic; phenyl, and 8-10-membered aryl. In someembodiments, R⁵ and R⁶ are each independently an optionally substitutedC₁₋₂₀ aliphatic. In some embodiments, R⁵ and R⁶ are each independentlyan optionally substituted C₁₋₂₀ heteroaliphatic having. In someembodiments, R⁵ and R⁶ are each independently an optionally substitutedphenyl or 8-10-membered aryl. In some embodiments, R⁵ and R⁶ are eachindependently an optionally substituted 5- to 10-membered heteroaryl. Insome embodiments, R³ and R⁴ can be taken together with intervening atomsto form one or more rings selected from the group consisting of:optionally substituted C₃-C₁₄ carbocycle, optionally substituted C₃-C₁₄heterocycle, optionally substituted C₆-C₁₀ aryl, and optionallysubstituted 5- to 10-membered heteroaryl. In some embodiments, R⁵ and R⁶are each independently an optionally substituted C₁₋₆ aliphatic. In someembodiments, each occurrence of R⁵ and R⁶ is independently methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In someembodiments, each occurrence of R⁵ and R⁶ is independently perfluoro. Insome embodiments, each occurrence of R⁵ and R⁶ is independently —CF₂CF₃.

In some embodiments, an activating functional group is

where R¹ and R² are as defined above.

In certain embodiments, R¹ and R² are each hydrogen. In someembodiments, only one of R¹ and R² is hydrogen. In certain embodiments,R¹ and R² are each independently an optionally substituted radicalselected from the group consisting of C₁₋₂₀ aliphatic; C₁₋₂₀heteroaliphatic, phenyl; a 3- to 8-membered saturated or partiallyunsaturated monocyclic carbocycle, a 7-14 carbon saturated, partiallyunsaturated or aromatic polycyclic carbocycle; a 5- to 6-memberedmonocyclic heteroaryl ring having 1-4 heteroatoms independently selectedfrom nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated orpartially unsaturated heterocyclic ring having 1-3 heteroatomsindependently selected from nitrogen, oxygen, or sulfur; a 6- to12-membered polycyclic saturated or partially unsaturated heterocyclehaving 1-5 heteroatoms independently selected from nitrogen, oxygen, orsulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5heteroatoms independently selected from nitrogen, oxygen, or sulfur.

In certain embodiments, R¹ and R² are each independently an optionallysubstituted radical selected from the group consisting of C₁₋₁₂aliphatic and C₁₋₁₂ heteroaliphatic. In some embodiments, eachoccurrence of R¹ and R² is independently an optionally substituted C₁₋₂₀aliphatic. In some embodiments, R¹ and R² are each independentlyoptionally substituted C₁₋₁₂ aliphatic. In some embodiments, R¹ and R²are each independently optionally substituted C₁₋₆ aliphatic. In someembodiments, each occurrence of R¹ and R² is independently an optionallysubstituted C₁₋₂₀ heteroaliphatic. In some embodiments, each occurrenceof R¹ and R² is independently an optionally substituted C₁₋₁₂heteroaliphatic. In some embodiments, each occurrence of R¹ and R² isindependently an optionally substituted phenyl or 8- to 10-memberedaryl. In some embodiments, each occurrence of R¹ and R² is independentlyan optionally substituted phenyl group. In some embodiments, eachoccurrence of R¹ and R² is independently an optionally substituted 5- to10-membered heteroaryl group. In some embodiments, each occurrence of R¹and R² is independently an optionally substituted 3- to 7-memberedheterocyclic.

In certain embodiments, R¹ and R² are each independently hydrogen,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionallysubstituted phenyl, or optionally substituted benzyl. In certainembodiments, R¹ and R² are both methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R¹ and R²are each butyl. In some embodiments, R¹ and R² are each isopropyl. Insome embodiments, R¹ and R² are perfluoro. In some embodiments, R¹ andR² are —CF₂CF₃. In some embodiments, R¹ and R² are each phenyl. In someembodiments, R¹ and R² are each benzyl.

In some embodiments, R¹ and R² are taken together with intervening atomsto form one or more optionally substituted rings. In certainembodiments, R¹ and R² are taken together to form a ring fragmentselected from the group consisting of: —C(R^(y))₂—,—C(R^(y))₂C(R^(y))₂—, —C(R^(y))₂C(R^(y))₂C(R^(y))₂—,—C(R^(y))₂OC(R^(y))₂—, and —C(R^(y))₂NR^(y)C(R^(y))₂—. In certainembodiments, R¹ and R² are taken together to form a ring fragmentselected from the group consisting of: —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—,—CH₂OCH₂—, and —CH₂NR^(y)CH₂—. In some embodiments, R¹ and R² are takentogether to form an unsaturated linker moiety optionally containing oneor more additional heteroatoms. In some embodiments, the resultingnitrogen-containing ring is partially unsaturated. In certainembodiments, the resulting nitrogen-containing ring comprises a fusedpolycyclic heterocycle.

In some embodiments, an activating functional group is

In certain embodiments, R¹, R², and R³ are each independently anoptionally substituted group selected from the group consisting of C₁₋₂₀aliphatic; C₁₋₂₀ heteroaliphatic; phenyl; and 8-10-membered aryl. Incertain embodiments, R¹, R², and R³ are each independently an optionallysubstituted 4-7-membered heterocyclic. In some embodiments, R¹ and R²can be taken together with intervening atoms to form one or more ringsselected from the group consisting of: optionally substituted C₃-C₁₄carbocycle, optionally substituted C₃-C₁₄ heterocycle, optionallysubstituted C₆-C₁₀ aryl, and optionally substituted 5- to 10-memberedheteroaryl. In certain embodiments, R¹, R², and R³ are eachindependently an optionally substituted C₁₋₆ aliphatic. In certainembodiments, R¹, R², and R³ are each independently selected from thegroup consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, or benzyl. In certain embodiments, R¹, R², and R³ are eachindependently perfluoro. In some embodiments, R¹, R², and R³ are eachindependently —CF₂CF₃.

In some embodiments, an activating functional group is

where R¹ and R² are as defined above.

In certain embodiments, R¹ and R² are each hydrogen. In someembodiments, only one of R¹ and R² is hydrogen. In certain embodiments,R¹ and R² are each independently an optionally substituted radicalselected from the group consisting of C₁₋₂₀ aliphatic; C₁₋₂₀heteroaliphatic, phenyl; a 3- to 8-membered saturated or partiallyunsaturated monocyclic carbocycle, a 7-14 carbon saturated, partiallyunsaturated or aromatic polycyclic carbocycle; a 5- to 6-memberedmonocyclic heteroaryl ring having 1-4 heteroatoms independently selectedfrom nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated orpartially unsaturated heterocyclic ring having 1-3 heteroatomsindependently selected from nitrogen, oxygen, or sulfur; a 6- to12-membered polycyclic saturated or partially unsaturated heterocyclehaving 1-5 heteroatoms independently selected from nitrogen, oxygen, orsulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5heteroatoms independently selected from nitrogen, oxygen, or sulfur.

In certain embodiments, R¹ and R² are each independently an optionallysubstituted radical selected from the group consisting of C₁₋₁₂aliphatic and C₁₋₁₂ heteroaliphatic. In some embodiments, eachoccurrence of R¹ and R² is independently an optionally substituted C₁₋₂₀aliphatic. In some embodiments, R¹ and R² are each independentlyoptionally substituted C₁₋₁₂ aliphatic. In some embodiments, R¹ and R²are each independently optionally substituted C₁₋₆ aliphatic. In someembodiments, each occurrence of R¹ and R² is independently an optionallysubstituted C₁₋₂₀ heteroaliphatic. In some embodiments, each occurrenceof R¹ and R² is independently an optionally substituted C₁₋₁₂heteroaliphatic. In some embodiments, each occurrence of R¹ and R² isindependently an optionally substituted 8- to 10-membered aryl. In someembodiments, each occurrence of R¹ and R² is independently an optionallysubstituted phenyl group. In some embodiments, each occurrence of R¹ andR² is independently an optionally substituted 5- to 10-memberedheteroaryl group. In some embodiments, each occurrence of R¹ and R² isindependently an optionally substituted 3- to 7-membered heterocyclic.

In certain embodiments, R¹ and R² are each independently hydrogen,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionallysubstituted phenyl, or optionally substituted benzyl. In certainembodiments, R¹ and R² are both methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R¹ and R²are each butyl. In some embodiments, R¹ and R² are each isopropyl. Insome embodiments, R¹ and R² are perfluoro. In some embodiments, R¹ andR² are —CF₂CF₃. In some embodiments, R¹ and R² are each phenyl. In someembodiments, R¹ and R² are each benzyl.

In some embodiments, R¹ and R² are taken together with intervening atomsto form one or more optionally substituted rings. In certainembodiments, R¹ and R² are taken together to form a ring fragmentselected from the group consisting of: —C(R^(y))₂—, —C(R′)₂C(R^(y))₂—,—C(R^(y))₂C(R^(y))₂C(R^(y))₂—, —C(R′)₂OC(R^(y))₂—, and—C(R^(y))₂NR^(y)C(R^(y))₂—. In certain embodiments, R¹ and R² are takentogether to form a ring fragment selected from the group consisting of:—CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—, —CH₂OCH₂—, and —CH₂NR^(y)CH₂—. In someembodiments, R¹ and R² are taken together to form an unsaturated linkermoiety optionally containing one or more additional heteroatoms. In someembodiments, the resulting nitrogen-containing ring is partiallyunsaturated. In certain embodiments, the resulting nitrogen-containingring comprises a fused polycyclic heterocycle.

In some embodiments, an activating functional group is

In certain embodiments, R¹ and R² are each independently an optionallysubstituted group selected from the group consisting of C₁₋₂₀ aliphatic;C₁₋₂₀ heteroaliphatic; phenyl; and 8-10-membered aryl. In someembodiments, R¹ and R² are each independently an optionally substituted4-7-membered heterocyclic. In some embodiments, R¹ and R² can be takentogether with intervening atoms to form one or more rings selected fromthe group consisting of: optionally substituted C₃-C₁₄ carbocycle,optionally substituted C₃-C₁₄ heterocycle, optionally substituted C₆-C₁₀aryl, and optionally substituted 5- to 10-membered heteroaryl. In someembodiments, R¹ and R² are each independently selected from the groupconsisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, or benzyl. In some embodiments, each occurrence of R¹ and R² isindependently perfluoro. In some embodiments, each occurrence of R¹ andR² is independently —CF₂CF₃.

In some embodiments, an activating functional group is

In certain embodiments, R¹, R², and R³ are each independently anoptionally substituted group selected from the group consisting of C₁₋₂₀aliphatic; C₁₋₂₀ heteroaliphatic; phenyl; and 8-10-membered aryl. Incertain embodiments, R¹, R², and R³ are each independently an optionallysubstituted 4-7-membered heterocyclic. In some embodiments, R¹ and R²can be taken together with intervening atoms to form one or more ringsselected from the group consisting of: optionally substituted C₃-C₁₄carbocycle, optionally substituted C₃-C₁₄ heterocycle, optionallysubstituted C₆-C₁₀ aryl, and optionally substituted 5- to 10-memberedheteroaryl. In certain embodiments, R¹, R², and R³ are eachindependently an optionally substituted C₁₋₆ aliphatic. In certainembodiments, R¹, R², and R³ are each independently selected from thegroup consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, or benzyl. In certain embodiments, R¹, R², and R³ are eachindependently perfluoro. In some embodiments, R¹, R², and R³ are eachindependently —CF₂CF₃.

In some embodiments, an activating functional group is

where R¹ and R² are as defined above.

In certain embodiments, R¹ and R² are each independently an optionallysubstituted group selected from the group consisting of C₁₋₂₀ aliphatic;C₁₋₂₀ heteroaliphatic; phenyl; and 8-10-membered aryl. In someembodiments, R¹ and R² are each independently an optionally substituted4-7-membered heterocyclic. In some embodiments, R¹ and R² can be takentogether with intervening atoms to form one or more rings selected fromthe group consisting of: optionally substituted C₃-C₁₄ carbocycle,optionally substituted C₃-C₁₄ heterocycle, optionally substituted C₆-C₁₀aryl, and optionally substituted 5- to 10-membered heteroaryl. In someembodiments, R¹ and R² are each independently selected from the groupconsisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, or benzyl. In some embodiments, each occurrence of R¹ and R² isindependently perfluoro. In some embodiments, each occurrence of R¹ andR² is independently CF₂CF₃.

In certain embodiments, X is any anion. In certain embodiments, X is anucleophile. In some embodiments, X is a nucleophile capable of ringopening an epoxide. In certain embodiments, X is absent. In certainembodiments, X is a nucleophilic ligand. Exemplary nucleophilic ligandsinclude, but are not limited to, —OR^(x), —SR^(x), —O(C═O)R^(x),—O(C═O)OR^(x), —O(C═O)N(R^(x))₂, —N(R^(x))(C═O)R^(x), —NC, —CN, halo(e.g., —Br, —I, —Cl), —N₃, —O(SO₂)R^(x) and —OPR^(x) ₃, wherein eachR^(x) is, independently, selected from hydrogen, optionally substitutedaliphatic, optionally substituted heteroaliphatic, optionallysubstituted aryl and optionally substituted heteroaryl.

In certain embodiments, X is —O(C═O)R^(x), wherein R^(x) is selectedfrom optionally substituted aliphatic, fluorinated aliphatic, optionallysubstituted heteroaliphatic, optionally substituted aryl, fluorinatedaryl, and optionally substituted heteroaryl.

For example, in certain embodiments, X is —O(C═O)R^(x), wherein R^(x) isoptionally substituted aliphatic. In certain embodiments, X is—O(C═O)R^(x), wherein R^(x) is optionally substituted alkyl andfluoroalkyl. In certain embodiments, X is —O(C═O)CH₃ or —O(C═O)CF₃.

Furthermore, in certain embodiments, X is —O(C═O)R^(x), wherein R^(x) isoptionally substituted aryl, fluoroaryl, or heteroaryl. In certainembodiments, X is —O(C═O)R^(x), wherein R^(x) is optionally substitutedaryl. In certain embodiments, X is —O(C═O)R^(x), wherein R^(x) isoptionally substituted phenyl. In certain embodiments, X is —O(C═O)C₆H₅or —O(C═O)C₆F₅.

In certain embodiments, X is —OR^(x), wherein R^(x) is selected fromoptionally substituted aliphatic, optionally substitutedheteroaliphatic, optionally substituted aryl, and optionally substitutedheteroaryl.

For example, in certain embodiments, X is —OR^(x), wherein R^(x) isoptionally substituted aryl. In certain embodiments, X is —OR^(x),wherein R^(x) is optionally substituted phenyl. In certain embodiments,X is —OC₆H₅ or —OC₆H₂(2,4-NO₂).

In certain embodiments, X is halo. In certain embodiments, X is —Br. Incertain embodiments, X is —Cl. In certain embodiments, X is —I.

In certain embodiments, X is —O(SO₂)R^(x). In certain embodiments X is—OTs. In certain embodiments X is —OSO₂Me. In certain embodiments X is—OSO₂CF₃. In some embodiments, X is a 2,4-dinitrophenolate anion.

I.c. Phosphorous-Containing Activating Groups

In some embodiments, activating functional groups Z are phosphorouscontaining groups.

In certain embodiments, a phosphorous-containing functional group ischosen from the group consisting of: phosphines (—PR^(y) ₂); Phosphineoxides —P(O)R^(y) ₂; phosphinites P(OR⁷)R^(y) ₂; phosphonitesP(OR⁷)₂R^(y); phosphites P(OR⁷)₃; phosphinates OP(OR⁷)R^(y) ₂;phosphonates; OP(OR⁷)₂R^(y); phosphates —OP(OR⁷)₃; phosponium salts([—PR^(y) ₃]⁺) where a phosphorous-containing functional group may belinked to a metal complex through any available position (e.g. directlinkage via the phosphorous atom, or in some cases via an oxygen atom).

In certain embodiments, a phosphorous-containing functional group ischosen from the group consisting of:

or a combination of two or more of these

-   -   wherein R¹ and R², are as defined above; and    -   each R^(7′), is independently hydrogen, a hydroxyl protecting        group, or an optionally substituted radical selected from the        group consisting of C₁₋₂₀ acyl; C₁₋₂₀ aliphatic; C₁₋₂₀        heteroaliphatic; phenyl; a 3- to 8-membered saturated or        partially unsaturated monocyclic carbocycle, a 7-14 carbon        saturated, partially unsaturated or aromatic polycyclic        carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having        1-4 heteroatoms independently selected from nitrogen, oxygen, or        sulfur; a 3- to 8-membered saturated or partially unsaturated        heterocyclic ring having 1-3 heteroatoms independently selected        from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic        saturated or partially unsaturated heterocycle having 1-5        heteroatoms independently selected from nitrogen, oxygen, or        sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having        1-5 heteroatoms independently selected from nitrogen, oxygen, or        sulfur; and where two R^(7′) groups can be taken together with        intervening atoms to form an optionally substituted ring        optionally containing one or more heteroatoms, and an R⁷ group        can be taken with an R¹ or R² group to an optionally substituted        ring;

In some embodiments, phosphorous containing functional groups includethose disclosed in The Chemistry of Organophosphorus Compounds. Volume4. Ter-and Quinquevalent Phosphorus Acids and their Derivatives. TheChemistry of Functional Group Series Edited by Frank R. Hartley(Cranfield University, Cranfield, U.K.). Wiley: New York. 1996. ISBN0-471-95706-2, the entirety of which is hereby incorporated herein byreference.*—(X)_(b)—[(R⁶R⁷R⁸P)⁺]_(n)Q^(n-), wherein:

-   X is —O—, —N═, or —NR^(z)—,-   b is 1 or 0,-   each of R⁶, R⁷ and R⁸ are independently present or absent and, if    present, are independently selected from the group consisting of    optionally substituted C₁-C₂₀ aliphatic, optionally substituted    phenyl, optionally substituted C₈₋C₁₄ aryl, optionally substituted    3- to 14-membered heterocyclic, optionally substituted 5- to    14-membered heteroaryl, halogen, ═O, —OR^(z), ═NR^(z), and N(R^(z))₂    where R^(z) is hydrogen, or an optionally substituted C₁-C₂₀    aliphatic, optionally substituted phenyl, optionally substituted 8-    to 14-membered aryl, optionally substituted 3- to 14-membered    heterocyclic, or optionally substituted 5- to 14-membered    heteroaryl,-   Q is any anion, and-   n is an integer between 1 and 4.

In some embodiments, an activating functional group is a phosphonategroup:

wherein R¹, R², and R^(7′) is as defined above.

In specific embodiments, a phosphonate activating functional group isselected from the group consisting of:

In some embodiments, an activating functional group is a phosphonicdiamide group:

wherein R¹, R², and R^(7′), are as defined above. In certainembodiments, each R¹ and R² group in a phosphonic diamide is methyl.

In some embodiments, an activating functional group is a phosphinegroup:

wherein R¹, and R² are as defined above.

In specific embodiments, a phosphine activating functional group isselected from the group consisting of:

II. Linker Moieties

As described above, each activating moiety

(Z)_(m) comprises a linker “

” coupled to at least one activating functional group Z as describedabove, with m denoting the number of activating functional groupspresent on a single linker moiety.

As noted above there may be one or more activating moiety

(Z)_(m) tethered to a given metal complex, similarly, each activatingmoiety itself may contain more than one activating functional group Z.In certain embodiments, each activating moiety contains only oneactivating functional group (i.e. m=1). In some embodiments, eachactivating moiety contains more than one activating functional groups(i.e. m>1). In certain embodiments, an activating moiety contains twoactivating functional groups (i.e. m=2). In certain embodiments, anactivating moiety contains three activating functional groups (i.e.m=3). In certain embodiments, an activating moiety contains fouractivating functional groups (i.e. m=4). In certain embodiments wheremore than one activating functional group is present on an activatingmoiety, they are all the same functional group. In some embodimentswhere more than one activating functional group is present on anactivating moiety, two or more of the activating functional groups aredifferent.

In certain embodiments, each linker moiety

contains 1-30 atoms including at least one carbon atom, and optionallyone or more atoms selected from the group consisting of N, O, S, Si, B,and P.

In certain embodiments, the linker is an optionally substituted C₂₋₃₀aliphatic group wherein one or more methylene units are optionally andindependently replaced by —NR^(y)—, —N(R^(y))C(O)—, —C(O)N(R^(y))—, —O—,—C(O)—, —OC(O)—, —C(O)O—, —S—, —SO—, —SO₂—, —C(═S)—, —C(═NR^(y))—, or—N═N—, where each occurrence of R^(y) is independently —H, or anoptionally substituted radical selected from the group consisting ofC₁₋₆ aliphatic 3- to 7-membered heterocyclic, phenyl, and 8- to10-membered aryl. In certain embodiments, a linker moiety is a C₄-C₁₂aliphatic group substituted with one or more moieties selected from thegroup consisting of halogen, —NO₂, —CN, —SR^(y), —S(O)R^(y),—S(O)₂R^(y), —NR^(y)C(O)R^(y), —OC(O)R, —CO₂R^(y), —NCO, —N₃, —OR⁷,—OC(O)N(R^(y))₂, —N(R^(y))₂, —NR^(y)C(O)R^(y), and —NR^(y)C(O)OR^(y),where R^(y) is —H, or an optionally substituted radical selected fromthe group consisting of C₁₋₆ aliphatic 3- to 7-membered heterocyclic,phenyl, and 8- to 10-membered aryl.

In certain embodiments, a linker moiety is an optionally substitutedC₃₋C₃₀ aliphatic group. In certain embodiments, a linker is anoptionally substituted C₄₋₂₄ aliphatic group. In certain embodiments, alinker moiety is an optionally substituted C₄-C₂₀ aliphatic group. Incertain embodiments, a linker moiety is an optionally substituted C₄-C₁₂aliphatic group. In certain embodiments, a linker is an optionallysubstituted C₄₋₁₀ aliphatic group. In certain embodiments, a linker isan optionally substituted C₄₋₈ aliphatic group. In certain embodiments,a linker moiety is an optionally substituted C₄-C₆ aliphatic group. Incertain embodiments, a linker moiety is an optionally substituted C₆-C₁₂aliphatic group. In certain embodiments, a linker moiety is anoptionally substituted C₈ aliphatic group. In certain embodiments, alinker moiety is an optionally substituted C₇ aliphatic group. Incertain embodiments, a linker moiety is an optionally substituted C₆aliphatic group. In certain embodiments, a linker moiety is anoptionally substituted C₅ aliphatic group. In certain embodiments, alinker moiety is an optionally substituted C₄ aliphatic group. Incertain embodiments, a linker moiety is an optionally substituted C₃aliphatic group. In certain embodiments, a aliphatic group in the linkermoiety is an optionally substituted straight alkyl chain. In certainembodiments, the aliphatic group is an optionally substituted branchedalkyl chain. In some embodiments, a linker moiety is a C₄ to C₂₀ alkylgroup having one or more methylene groups replaced by —C(R^(a)R^(b))—where R^(a) and R^(b) are each, independently C₁-C₄ alkyl groups. Incertain embodiments, a linker moiety consists of an aliphatic grouphaving 4 to 30 carbons including one or more gem-dimethyl substitutedcarbon atoms.

In certain embodiments, a linker moiety includes one or more optionallysubstituted cyclic elements selected from the group consisting ofsaturated or partially unsaturated carbocyclic, aryl, heterocyclic, orheteroaryl. In certain embodiments, a linker moiety consists of thesubstituted cyclic element, in some embodiments the cyclic element ispart of a linker with one or more non-ring heteroatoms or optionallysubstituted aliphatic groups comprising other parts of the linkermoiety.

In some embodiments, a linker moiety is of sufficient length to allowone or more activating functional groups to be positioned near a metalatom of a metal complex. In certain embodiments, structural constraintsare built into a linker moiety to control the disposition andorientation of one or more activating functional groups near a metalcenter of a metal complex. In certain embodiments such structuralconstraints are selected from the group consisting of cyclic moieties,bicyclic moieties, bridged cyclic moieties and tricyclic moieties. Insome embodiments, such structural constraints are the result of acyclicsteric interactions. In certain embodiments such structural constraintsare selected from the group consisting of cis double bonds, trans doublebonds, cis allenes, trans allenes, and triple bonds. In someembodiments, such structural constraints are selected from the groupconsisting of substituted carbons including geminally disubstitutedgroups such as sprirocyclic rings, gem dimethyl groups, gem diethylgroups and gem diphenyl groups. In certain embodiments such structuralconstraints are selected from the group consisting ofheteratom-containing functional groups such as sulfoxides, amides, andoximes.

In certain embodiments, linker moieties are selected from the groupconsisting of:

where * represents the site of attachment to a ligand, and each #represents a site of attachment of an activating functional group.

In some embodiments, s is 0. In some embodiments, s is 1. In someembodiments, s is 2. In some embodiments, s is 3. In some embodiments, sis 4. In some embodiments, s is 5. In some embodiments, s is 6.

In some embodiments, t is 1. In some embodiments, t is 2. In someembodiments, t is 3. In some embodiments, t is 4.

III. Metal Complexes

As noted above, the present invention encompasses metal complexes thatinclude a metal atom coordinated to a multidentate ligand and at leastone activating moiety tethered to a multidentate ligand. In certainembodiments, provided metal complexes have the structure:

where

represents a metal atom coordinated to a multidentate ligand.III.a. Metal Atoms

In certain embodiments, M is a metal atom selected from periodic tablegroups 3-13, inclusive. In certain embodiments, M is a transition metalselected from periodic table groups 5-12, inclusive. In certainembodiments, M is a transition metal selected from periodic table groups4-11, inclusive. In certain embodiments, M is a transition metalselected from periodic table groups 5-10, inclusive. In certainembodiments, M is a transition metal selected from periodic table groups7-9, inclusive. In some embodiments, M is selected from the groupconsisting of Cr, Mn, V, Fe, Co, Mo, W, Ru, Al, and Ni. In someembodiments, M is a metal atom selected from the group consisting of:cobalt; chromium; aluminum; titanium; ruthenium, and manganese. In someembodiments, M is cobalt. In some embodiments, M is chromium. In someembodiments, M is aluminum.

In certain embodiments, a metal complex is a zinc, cobalt, chromium,aluminum, titanium, ruthenium, or manganese complex. In certainembodiments, a metal complex is an aluminum complex. In someembodiments, a metal complex is a chromium complex. In some embodiments,a metal complex is a zinc complex. In certain some embodiments, a metalcomplex is a titanium complex. In some embodiments, a metal complex is aruthenium complex. In certain embodiments, a metal complex is amanganese complex. In certain embodiments, a metal complex is cobaltcomplex. In certain embodiments where the metal complex is a cobaltcomplex, the cobalt metal has an oxidation state of 3+(i.e., Co(III)).In some embodiments, the cobalt metal has an oxidation state of 2+.

III.b. Ligands

In some embodiments, a metal complex

comprises a metal atom coordinated to a single tetradentate ligand andin some embodiments, the metal complex comprises a chelate containing aplurality of individual ligands. In certain embodiments, a metal complexcontains two bidentate ligands. In some embodiments, a metal complexcontains a tridentate ligand.

In various embodiments, tetradentate ligands suitable for metalcomplexes of the present invention may include, but are not limited to:salen derivatives 1, derivatives of salan ligands 2,bis-2-hydroxybenzamido derivatives 3, derivatives of the i ligand 4,porphyrin derivatives 5, derivatives of tetrabenzoporphyrin ligands 6,derivatives of corrole ligands 7, phthalocyaninate derivatives 8, anddibenzotetramethyltetraaza[14]annulene (tmtaa) derivatives 9 or 9′.

In some embodiments, a metal multidentate ligand coordinated with ametal complex may comprise a plurality of discrete ligands. In someembodiments, metal complexes include two bidentate ligands. In certainembodiments, such bidentate ligands may have the structure

where R^(d) and R¹ are as defined above. Metal complexes having two suchligands may adopt one of several geometries, and the present disclosureencompasses such variations.

In certain embodiments, metal complexes including two bidentate ligandsmay have structures selected from the group consisting of:

where each

represents a ligand:

In certain embodiments, a tetradentate ligand is a salen ligand. Incertain embodiments, a metal complex is a metallosalenate. In certainembodiments, a metal complex is a cobalt salen complex. In certainembodiments, a metal complex is a chromium salen complex. In someembodiments, a metal complex is an aluminum salen complex.

In certain embodiments, at least one activating moiety is tethered to acarbon atom of a phenyl ring of the salicylaldehyde-derived portions ofa salen ligand. In certain embodiments, at least one activating moietyis tethered to a carbon atom of a porphyrin ligand. In certainembodiments, at least one activating moiety is tethered to apyrrole-carbon atom of a porphyrin ligand. In certain embodiments, atleast one activating moiety is tethered to a carbon atom forming thebridge between the pyrrole rings of a porphyrin ligand.

In certain embodiments, at least one activating moiety is tethered toone or more carbon atoms of only one phenyl ring of thesalicylaldehyde-derived portions of a salen ligand, as shown in formulaI:

wherein:

-   -   M is a metal atom;    -   X is a nucleophile capable of ring opening an epoxide;    -   k is an integer from 0-2 inclusive;    -   R′ represents one or more substituents optionally present on the        phenyl rings and each R′ is independently selected from the        group consisting of: halogen, —NO₂, —CN, —SR^(y), —S(O)R^(y),        —S(O)₂R^(y), —NR^(y)C(O)R, —OC(O)R^(y), —CO₂R^(y), —NCO, —N₃,        —OR⁷, —OC(O)N(R^(y))₂, —N(R^(y))₂, —NR^(y)C(O)R^(y),        —NR^(y)C(O)OR^(y); or an optionally substituted radical selected        from the group consisting of C₁₋₂₀ aliphatic; C₁₋₂₀        heteroaliphatic; phenyl; a 3- to 8-membered saturated or        partially unsaturated monocyclic carbocycle, a 7-14 carbon        saturated, partially unsaturated or aromatic polycyclic        carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having        1-4 heteroatoms independently selected from nitrogen, oxygen, or        sulfur; a 3- to 8-membered saturated or partially unsaturated        heterocyclic ring having 1-3 heteroatoms independently selected        from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic        saturated or partially unsaturated heterocycle having 1-5        heteroatoms independently selected from nitrogen, oxygen, or        sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having        1-5 heteroatoms independently selected from nitrogen, oxygen, or        sulfur, where two or more adjacent R′ groups can be taken        together to form an optionally substituted saturated, partially        unsaturated, or aromatic 5- to 12-membered ring containing 0 to        4 heteroatoms;    -   R^(y) is —H, or an optionally substituted radical selected from        the group consisting of C₁₋₆ aliphatic, 3- to 7-membered        heterocyclic, phenyl, and 8- to 10-membered aryl;

represents is an optionally substituted moiety linking the two nitrogenatoms of the diamine portion of the salen ligand, where

is selected from the group consisting of phenyl; a 3- to 8-memberedsaturated or partially unsaturated monocyclic carbocycle, a 7-14 carbonsaturated, partially unsaturated or aromatic polycyclic carbocycle; a 5-to 6-membered monocyclic heteroaryl ring having 1-4 heteroatomsindependently selected from nitrogen, oxygen, or sulfur; a 3- to8-membered saturated or partially unsaturated heterocyclic ring having1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur;a 6- to 12-membered polycyclic saturated or partially unsaturatedheterocycle having 1-5 heteroatoms independently selected from nitrogen,oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ringhaving 1-5 heteroatoms independently selected from nitrogen, oxygen, orsulfur; or an optionally substituted C₂₋₂₀ aliphatic group, wherein oneor more methylene units are optionally and independently replaced by—NR^(y)—, —N(R^(y))C(O)—, —C(O)N(R^(y))—, —OC(O)N(R^(y))—,—N(R^(y))C(O)O—, —OC(O)O—, —O—, —C(O)—, —OC(O)—, —C(O)O—, —S—, —SO—,—SO₂—, —C(═S)—, —C(═NR^(y))—, —C(═NOR^(y))— or —N═N—;

-   -   (Z)_(m) represents one or more activating moieties, where “        ” is a covalent linker containing one or more atoms selected        from the group consisting of C, O, N, S, and Si; Z is a        activating functional group and m is an integer from 1 to 4        indicating the number of individual activating functional groups        present in each activating moiety.

In certain embodiments, both salicylaldehyde-derived portions of a salenligand bear one or more activating moieties:

wherein M, X, k, R′,

and

(Z)_(m) are as defined above.

In some embodiments, provided metal complexes comprise a

moiety that has the structure:

wherein:

-   -   M is a metal atom,    -   R^(1a), R^(1a′), R^(2a), R^(2a′), R^(3a), and R^(3a′) are        independently a        (Z)_(m) group, hydrogen, halogen, —OR, —NR₂, —SR, —CN, —NO₂,        —SO₂R, —SOR, —SO₂NR₂; —CNO, —NRSO₂R, —NCO, —N₃, —SiR₃; or an        optionally substituted radical selected from the group        consisting of C₁₋₂₀ aliphatic; C₁₋₂₀ heteroaliphatic; phenyl; a        3- to 8-membered saturated or partially unsaturated monocyclic        carbocycle, a 7-14 carbon saturated, partially unsaturated or        aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic        heteroaryl ring having 1-4 heteroatoms independently selected        from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated        or partially unsaturated heterocyclic ring having 1-3        heteroatoms independently selected from nitrogen, oxygen, or        sulfur; a 6- to 12-membered polycyclic saturated or partially        unsaturated heterocycle having 1-5 heteroatoms independently        selected from nitrogen, oxygen, or sulfur; or an 8- to        10-membered bicyclic heteroaryl ring having 1-5 heteroatoms        independently selected from nitrogen, oxygen, or sulfur; each R        is independently hydrogen, an optionally substituted radical        selected the group consisting of acyl; carbamoyl; arylalkyl;        phenyl, 8- to 10-membered aryl; C₁₋₁₂ aliphatic; C₁₋₁₂        heteroaliphatic; 5- to 10-membered heteroaryl; 4- to 7-membered        heterocyclyl; an oxygen protecting group; and a nitrogen        protecting group; or:        -   two R on the same nitrogen atom are taken with the nitrogen            to form a 3- to 7-membered heterocyclic ring;    -   wherein any of [R^(2a′) and R^(3a′)], [R^(2a) and R^(3a)],        [R^(1a) and R^(2a)], and [R^(1a′) and R^(2a′)] may optionally be        taken together with the carbon atoms to which they are attached        to form one or more rings which may in turn be substituted with        one or more R^(20a) groups; and    -   R^(4a) is selected from the group consisting of:

where

-   -   R^(c) at each occurrence is independently a        Z group, hydrogen, halogen, —OR, —NR₂, —SR, —CN, —NO₂, —SO₂R,        —SOR, —SO₂NR₂; —CNO, —NRSO₂R, —NCO, —N₃, —SiR₃; or an optionally        substituted radical selected from the group consisting of C₁₋₂₀        aliphatic; C₁₋₂₀ heteroaliphatic; phenyl; a 3- to 8-membered        saturated or partially unsaturated monocyclic carbocycle, a 7-14        carbon saturated, partially unsaturated or aromatic polycyclic        carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having        1-4 heteroatoms independently selected from nitrogen, oxygen, or        sulfur; a 3- to 8-membered saturated or partially unsaturated        heterocyclic ring having 1-3 heteroatoms independently selected        from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic        saturated or partially unsaturated heterocycle having 1-5        heteroatoms independently selected from nitrogen, oxygen, or        sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having        1-5 heteroatoms independently selected from nitrogen, oxygen, or        sulfur;        -   where:            -   two or more Re groups may be taken together with the                carbon atoms to which they are attached and any                intervening atoms to form one or more rings;            -   when two Re groups are attached to the same carbon atom,                they may be taken together along with the carbon atom to                which they are attached to form a moiety selected from                the group consisting of: a 3- to 8-membered spirocyclic                ring, a carbonyl, an oxime, a hydrazone, an imine;    -   X is a nucleophile capable of ring opening an epoxide;    -   Y is a divalent linker selected from the group consisting of:        —NR—, —N(R)C(O)—, —C(O)NR—, —O—, —C(O)—, —OC(O)—, —C(O)O—, —S—,        —SO—, —SO₂—, —C(═S)—, —C(═NR)—, or —N═N—; a polyether; a C₃ to        C₈ substituted or unsubstituted carbocycle; and a C₁ to C₈        substituted or unsubstituted heterocycle;    -   m′ is 0 or an integer from 1 to 4, inclusive;    -   q is 0 or an integer from 1 to 4, inclusive; and    -   x is 0, 1, or 2.

In some embodiments, at least one of [R^(2a) and R^(3a)] and [R^(2a′)and R^(3a′)] are taken together to form a ring. In some embodiments,both [R^(2a) and R^(3a)] and [R^(2a′) and R^(3a′)] are taken together toform rings. In some embodiments, the rings formed by [R^(2a) and R^(3a)]and [R^(2a′) and R^(3a′)] are substituted phenyl rings.

In certain embodiments, one or more of R^(1a), R^(1a′), R^(2a), R^(2a′),R^(3a), and R^(3a′) are independently a

Z group.

In certain embodiments of provided metal complexes, a

moiety has a structure selected from the group consisting of:

wherein:

-   -   M is a metal atom;    -   R^(4a), R^(4a′), R^(5a), R^(5a′), R^(6a), R^(6a′), R^(7a), and        R^(7a′) are each independently a        Z group, hydrogen, halogen, —OR, —NR₂, —SR, —CN, —NO₂, —SO₂R,        —SOR, —SO₂NR₂; —CNO, —NRSO₂R, —NCO, —N₃, —SiR₃; or an optionally        substituted radical selected from the group consisting of C₁₋₂₀        aliphatic; C₁₋₂₀ heteroaliphatic; phenyl; a 3- to 8-membered        saturated or partially unsaturated monocyclic carbocycle, a 7-14        carbon saturated, partially unsaturated or aromatic polycyclic        carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having        1-4 heteroatoms independently selected from nitrogen, oxygen, or        sulfur; a 3- to 8-membered saturated or partially unsaturated        heterocyclic ring having 1-3 heteroatoms independently selected        from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic        saturated or partially unsaturated heterocycle having 1-5        heteroatoms independently selected from nitrogen, oxygen, or        sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having        1-5 heteroatoms independently selected from nitrogen, oxygen, or        sulfur;    -   wherein [R^(1a) and R^(4a)], [R^(1a′) and R^(4a′)] and any two        adjacent R^(4a), R^(4a′), R^(5a), R^(5a′), R^(6a), R^(6a′),        R^(7a), and R^(7a′) groups can be taken together with        intervening atoms to form one or more optionally substituted        rings;    -   n is 0 or an integer from 1 to 8, inclusive; and    -   p is 0 or an integer from 1 to 4, inclusive.

In some embodiments, M is Co.

In some embodiments, R^(1a), R^(1a′), R^(4a), R^(4a′), R^(6a), andR^(6a′) are each —H. In some embodiments, R^(5a), R^(5a′), R^(7a) andR^(7a′) are each optionally substituted C₁-C₁₂ aliphatic. In someembodiments, R^(4a), R^(4a′), R^(5a), R^(5a′), R^(6a), R^(6a′), R^(7a),and R^(7a′) are each independently selected from the group consistingof: —H, —SiR₃; methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl,t-butyl, isoamyl, t-amyl, thexyl, and trityl. In some embodiments,R^(1a), R^(1a′), R^(4a), R^(4a′), R^(6a), and R^(6a′) are each —H. Insome embodiments, R^(7a) is selected from the group consisting of —H;methyl; ethyl; n-propyl; i-propyl; n-butyl; sec-butyl; t-butyl; isoamyl;t-amyl; thexyl; and trityl. In some embodiments, R^(5a) and R^(7a) areindependently selected from the group consisting of —H; methyl; ethyl;n-propyl; i-propyl; n-butyl; sec-butyl; t-butyl; isoamyl; t-amyl;thexyl; and trityl. In certain embodiments, one or more of R⁵, R^(5a′),R^(7a) and R^(7a′) is a

Z group. In some embodiments, R^(5a) and R^(5a′) are a

Z group.

In certain embodiments of provided metal complexes, a

moiety has a structure selected from the group consisting of:

In certain embodiments of complexes having formulae described above, atleast one of the phenyl rings comprising a salicylaldehyde-derivedportion of a catalyst is independently selected from the groupconsisting of:

where

(Z)_(m) represents one or more independently-defined activating moietieswhich may be bonded to any one or more unsubstituted positions of asalicylaldehyde-derived phenyl ring.

In certain embodiments, there is an activating moiety tethered to theposition ortho to a metal-bound oxygen substituent of one or both of thesalicylaldehyde-derived phenyl rings of a salen ligand as in formulaeIIIa and IIIb:

wherein:

-   -   M, X, k, R′,

and

(Z)_(m) are as defined above, and

-   -   R^(4a), R^(4a′), R^(5a), R^(5a′), R^(6a), and R^(6a′) are each        independently a        Z group, hydrogen, halogen, —OR, —NR₂, —SR, —CN, —NO₂, —SO₂R,        —SOR, —SO₂NR₂; —CNO, —NRSO₂R, —NCO, —N₃, —SiR₃; or an optionally        substituted radical selected from the group consisting of C₁₋₂₀        aliphatic; C₁₋₂₀ heteroaliphatic; phenyl; a 3- to 8-membered        saturated or partially unsaturated monocyclic carbocycle, a 7-14        carbon saturated, partially unsaturated or aromatic polycyclic        carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having        1-4 heteroatoms independently selected from nitrogen, oxygen, or        sulfur; a 3- to 8-membered saturated or partially unsaturated        heterocyclic ring having 1-3 heteroatoms independently selected        from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic        saturated or partially unsaturated heterocycle having 1-5        heteroatoms independently selected from nitrogen, oxygen, or        sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having        1-5 heteroatoms independently selected from nitrogen, oxygen, or        sulfur;    -   wherein any two adjacent R^(4a), R^(4a′), R^(5a), R^(5a′),        R^(6a), and R^(6a′) groups can be taken together with        intervening atoms to form one or more optionally substituted        rings.

In certain embodiments of compounds having formulae IIIa or IIIb,R^(4a), R^(4a′), R^(6a), and R^(6a′) are each hydrogen, and R^(5a),R^(5a′) are, independently, optionally substituted C₁-C₂₀ aliphatic.

In certain embodiments of complexes IIIa and IIIb, at least one of thephenyl rings comprising a salicylaldehyde-derived portion of a catalystis independently selected from the group consisting of:

In certain embodiments, there is an activating moiety tethered to theposition para to the phenolic oxygen of one or both of asalicylaldehyde-derived phenyl rings of the salen ligand as instructures IVa and IVb:

where M, X, k, R′, R^(4a), R^(4a′), R^(6a), R^(6a′), R^(7a), R^(7a′),

and

(Z)_(m) are as defined above.

In certain embodiments of compounds having formulae IVa or IVb, R^(4a),R^(4a′), R^(6a), and R^(6a′) are hydrogen, and each R^(7a), R^(7a′) is,independently, optionally substituted C₁-C₂₀ aliphatic.

In certain embodiments of catalysts IVa and IVb, at least one of thephenyl rings comprising a salicylaldehyde-derived portion of a catalystis independently selected from the group consisting of:

In some embodiments, there is an activating moiety tethered to theposition para to the imine substituent of one or both of thesalicylaldehyde-derived phenyl rings of a salen ligand as in formulae Vaor Vb:

where M, X, k, R′, R^(4a), R^(4a′), R^(5a), R^(5a′), R^(7a), R^(7a′),

and

(Z)_(m) are as defined above.

In certain embodiments of compounds having formulae Va or Vb, each R⁴and R^(4a) is hydrogen, and each R^(5a), R^(5a′), R^(7a), R^(7a′) is,independently, hydrogen or optionally substituted C₁-C₂₀ aliphatic.

In certain embodiments of catalysts Va and Vb, at least one of thephenyl rings comprising a salicylaldehyde-derived portion of a catalystis independently selected from the group consisting of:

In some embodiments, there is an activating moiety tethered to theposition ortho to the imine substituent of one or both of thesalicylaldehyde-derived phenyl rings of a salen ligand as in formulaeVIa and VIb:

where X, k, M, R′, R^(5a), R^(5a′), R^(6a), R^(6a′), R^(7a), R^(7a′),

and

(Z) are as defined above.

In certain embodiments of compounds having formulae VIa or VIb, eachR^(6a) and R^(6a′) is hydrogen, and each R^(5a), R^(5a′), R^(7a), andR^(7′) is, independently, hydrogen or optionally substituted C₁-C₂₀aliphatic.

In certain embodiments of catalysts VIa and VIb, at least one of thephenyl rings comprising a salicylaldehyde-derived portion of a catalystis independently selected from the group consisting of:

In some embodiments, there are activating moieties tethered to thepositions ortho and para to the phenolic oxygen of one or both of thesalicylaldehyde-derived phenyl rings of a salen ligand as in formulaeVIIa and VIIb:

where M, X, k, R′, R^(4a), R^(4a′), R^(6a), R^(6a′),

and

(Z)_(m) are as defined above.

In certain embodiments of compounds having formulae VIa or VIb, eachR^(6a), R^(6a′), R^(4a), and R^(4a′) is, independently, hydrogen oroptionally substituted C₁-C₂₀ aliphatic.

In certain embodiments of compounds having formulae VIIa or VIIb, eachR^(6a), R^(6a′), R^(4a), and R^(4a′) is hydrogen.

In some embodiments, there are activating moieties tethered to thepositions ortho and para to the imine substituent of one or both of thesalicylaldehyde-derived phenyl rings of a salen ligand as in formulaeVIIIa and VIIIb:

where X, k, M, R′, R^(5a), R^(5a′), R^(7a), R^(7a′),

and

(Z)_(m) are as defined above.

In certain embodiments of compounds having formulae VIIIa or VIIIb, eachR^(5a), R^(5a′), R^(7a), and R^(7a′) is, independently, optionally,hydrogen or substituted C₁-C₂₀ aliphatic.

In certain embodiments of the present invention, catalysts of structuresVIIIa or VIIIb above, at least one of the phenyl rings comprising thesalicylaldehyde-derived portion of a catalyst is independently selectedfrom the group consisting of:

In some embodiments, there is an activating moiety tethered to the iminecarbon of a salen ligand as in formulae IXa and IXb:

where M, X, k, M, R^(4a), R^(4a′), R^(5a), R^(5a′), R^(6a), R^(6a′),R^(7a), R^(7a′),

and

(Z)_(m) are as defined above with the proviso that the atom of theactivating moiety attached to the salen ligand is a carbon atom.

In certain embodiments of compounds having formulae IXa or IXb, eachR^(4a), R^(4a′), R^(6a), and R^(6a′) is hydrogen, and each R^(5a),R^(5a′), R^(7a), and R^(7a′) is, independently, hydrogen or optionallysubstituted C₁-C₂₀ aliphatic.

In certain embodiments of the present invention, catalysts of structuresVIIIa or IXa or IXb above, at least one of the phenyl rings comprisingthe salicylaldehyde-derived portion of a catalyst is independentlyselected from the group consisting of:

As shown above, the two phenyl rings derived from salicylaldehyde in thecore salen structures need not be the same. Though not explicitly shownin formulae Ia through IXb above, it is to be understood that a catalystmay have an activating moiety attached to different positions on each ofthe two rings, and such compounds are specifically encompassed withinthe scope of the present invention. Furthermore, activating moieties canbe present on multiple parts of the ligand, for instance activatingmoieties can be present on the diamine bridge and on one or both phenylrings in the same catalyst.

In certain embodiments, the salen ligand cores of catalysts Ia throughIXb above are selected from the group shown below wherein any availableposition may be independently substituted with one or more R-groups orone or more activating moieties as described above.

where M, X, and k, are as defined above.

In some embodiments, at least one activating moiety is tethered to thediamine-derived portion of the salen ligand, as shown in formula X:

where M, X, k, R′,

and

(Z)_(m) are as defined above.

In certain embodiments, salen ligands of formula X are selected from anoptionally substituted moiety consisting of:

where M, X, k, R′, and

(Z)_(m) are as defined above.

In certain embodiments, the diamine bridge of catalysts of formula Xa anoptionally substituted moiety selected from the group consisting of:

where M and

(Z)_(m) is as defined above.

In certain embodiments, metallosalenate complexes of the presentinvention include, but are not limited to those in Table 1 below:

TABLE 1

In certain embodiments, for complexes of Table 1, M is Co—X, where X isas defined above. In certain embodiments, for complexes of Table 1, M isCo—OC(O)CF₃. In certain embodiments, for complexes of Table 1, M isCo—OAc. In certain embodiments, for complexes of Table 1, M isCo—OC(O)C₆F₅. In certain embodiments, for complexes of Table 1, M isCo—N₃. In certain embodiments, for complexes of Table 1, M is Co—Cl. Incertain embodiments, for complexes of Table 1, M is Co-nitrophenoxy. Incertain embodiments, for complexes of Table 1, M is Co-dinitrophenoxy.

In some embodiments, for complexes of Table 1, M is Cr—X, where X is asdefined above.

In certain embodiments, a tetradentate ligand is a porphyrin ligand. Insome embodiments, a metal complex is a cobalt porphyrin complex. Incertain embodiments, a metal complex is a chromium porphyrin complex. Insome embodiments, a metal complex is an aluminum porphyrin complex.

Examples of porphyrin containing metal complexes of the presentinvention include, but are not limited to:

wherein each of M, X, k, R′, and

(Z)_(m) is as defined above.

In certain embodiments, a multidentate ligand is an optionallysubstituted tetrabenzoporphyrin. Suitable examples include, but are notlimited to:

wherein M, R′, and

(Z)_(n) are as previously defined.

In certain embodiments of porphyrin and phthalocyanine-based complexesdescribed herein, M is aluminum. In certain embodiments of porphyrin andphthalocyanine-based complexes described herein, M is cobalt. In certainembodiments of porphyrin and phthalocyanine-based complexes describedherein, M is manganese.

In certain embodiments, porphyrin complexes of the present inventioninclude, but are not limited to those in Table 2 below:

TABLE 2

In certain embodiments, for complexes of Table 2, M is Co—X, where X isas defined above. In certain embodiments, for complexes of Table 2, M isCo—OC(O)CF₃. In certain embodiments, for complexes of Table 2, M isCo—OAc. In certain embodiments, for complexes of Table 1, M isCo—OC(O)C₆F₅. In certain embodiments, for complexes of Table 2, M isCo—N₃. In certain embodiments, for complexes of Table 2, M is Co—Cl. Incertain embodiments, for complexes of Table 2, M is Co-nitrophenoxy. Incertain embodiments, for complexes of Table 2, M is Co-dinitrophenoxy.

In certain embodiments, for complexes of Table 2, M is Al—X, where X isas defined above. In certain embodiments, for complexes of Table 2, M isCr—X, where X is as defined above.

In certain embodiments, porphyrin complexes of the present invention aresynthesized as shown in the following schemes:

In some embodiments, the present disclosure provides methods ofpolymerization comprising contacting an epoxide with carbon dioxide inthe presence of a provided metal complex to form a polycarbonate. Insome embodiments, the present invention provides a method ofpolymerization, the method comprising:

-   -   a) providing an epoxide of formula:

-   -   -   wherein:        -   R^(a′) is hydrogen or an optionally substituted radical            selected from the group consisting of C₁₋₃₀ aliphatic; C₁₋₃₀            heteroaliphatic; phenyl; a 3- to 8-membered saturated or            partially unsaturated monocyclic carbocycle, a 7-14 carbon            saturated, partially unsaturated or aromatic polycyclic            carbocycle; a 5- to 6-membered monocyclic heteroaryl ring            having 1-4 heteroatoms independently selected from nitrogen,            oxygen, or sulfur; a 3- to 8-membered saturated or partially            unsaturated heterocyclic ring having 1-3 heteroatoms            independently selected from nitrogen, oxygen, or sulfur; a            6- to 12-membered polycyclic saturated or partially            unsaturated heterocycle having 1-5 heteroatoms independently            selected from nitrogen, oxygen, or sulfur; or an 8- to            10-membered bicyclic heteroaryl ring having 1-5 heteroatoms            independently selected from nitrogen, oxygen, or sulfur; and        -   each of R^(b′), R^(c′), and R^(d′) is independently hydrogen            or an optionally substituted radical selected from the group            consisting of C₁₋₁₂ aliphatic; C₁₋₁₂ heteroaliphatic;            phenyl; a 3- to 8-membered saturated or partially            unsaturated monocyclic carbocycle, a 7-14 carbon saturated,            partially unsaturated or aromatic polycyclic carbocycle; a            5- to 6-membered monocyclic heteroaryl ring having 1-4            heteroatoms independently selected from nitrogen, oxygen, or            sulfur; a 3- to 8-membered saturated or partially            unsaturated heterocyclic ring having 1-3 heteroatoms            independently selected from nitrogen, oxygen, or sulfur; a            6- to 12-membered polycyclic saturated or partially            unsaturated heterocycle having 1-5 heteroatoms independently            selected from nitrogen, oxygen, or sulfur; or an 8- to            10-membered bicyclic heteroaryl ring having 1-5 heteroatoms            independently selected from nitrogen, oxygen, or sulfur;        -   wherein any of (R^(a′) and R^(c′)), (R^(c′) and R^(d′)), and            (R^(a′) and R^(b′)) can be taken together with intervening            atoms to form one or more optionally substituted rings;

    -   b) contacting the epoxide and carbon dioxide in the presence of        a metal complex as described herein to provide a polymer having        a formula selected from the group consisting of:

In some embodiments, a provided polymer has a formula:

In some embodiments, a provided polymer has a formula:

In some embodiments, carbon dioxide is optional and a provided polymerhas a formula:

In certain embodiments, R^(b′), R^(c′), and R^(d′) are each hydrogen. Insome embodiments, R^(a′) is optionally substituted C₁₋₁₂ aliphatic. Insome embodiments, R^(a′) is optionally substituted C₁₋₁₂heteroaliphatic. In some embodiments, the epoxide is ethylene oxide,propylene oxide, or cyclohexene oxide.

In certain embodiments, one of R^(a′), R^(b′), R^(c′), and R^(d′) ishydrogen. In certain embodiments, two of R^(a′), R^(b′), R^(c′), andR^(d′) are hydrogen. In certain embodiments, three of R^(a′), R^(b′),R^(c′), and R^(d′) are hydrogen.

In certain embodiments, R^(a′) is hydrogen. In certain embodiments,R^(b′) is hydrogen. In certain embodiments, R^(c′) is hydrogen. Incertain embodiments, R^(d′) is hydrogen.

In certain embodiments, R^(a′), R^(b′), R^(c′), and R^(d′) are eachindependently an optionally substituted C₁₋₃₀ aliphatic group. Incertain embodiments, R^(a′), R^(b′), R^(c′), and R^(d′) are eachindependently an optionally substituted C₁₋₂₀ aliphatic group. Incertain embodiments, R^(a′), R^(b′), R^(c′), and R^(d′) are eachindependently an optionally substituted C₁₋₁₂ aliphatic group. Incertain embodiments, R^(a′), R^(b′), R^(c′), and R^(d′) are eachindependently an optionally substituted C₁₋₈ aliphatic group. In certainembodiments, R^(a′), R^(b′), R^(c′), and R^(d′) are each independentlyan optionally substituted C₃₋₈ aliphatic group. In certain embodiments,R^(a′), R^(b′), R^(c′), and R^(d′) are each independently an optionallysubstituted C₃₋₁₂ aliphatic group.

In certain embodiments, R^(a′) is an optionally substituted C₁₋₃₀aliphatic group. In certain embodiments, R^(b′) is an optionallysubstituted C₁₋₃₀ aliphatic group. In certain embodiments, R^(c′) is anoptionally substituted C₁₋₃₀ aliphatic group. In certain embodiments,R^(d′) is an optionally substituted C₁₋₃₀ aliphatic group.

In some embodiments, an R^(a′) and an R^(b′) attached to the same carbonare taken together to form one or more optionally substituted3-12-membered carbocyclic rings. In some embodiments, an R^(a′) and anR^(b′) attached to the same carbon are taken together to form apolycyclic carbocycle comprising two or more optionally substituted3-8-membered carbocyclic rings. In some embodiments, an R^(a′) and anR^(b′) attached to the same carbon are taken together to form apolycyclic carbocycle comprising two or more optionally substituted5-7-membered carbocyclic rings.

In some embodiments, an R^(a′) and an R^(b′) attached to the same carbonare taken together to form a bicyclic carbocycle comprising twooptionally substituted 3-12-membered carbocyclic rings. In someembodiments, an R^(a′) and an R^(b′) attached to the same carbon aretaken together to form a bicyclic carbocycle comprising two optionallysubstituted 3-8-membered carbocyclic rings. In some embodiments, anR^(a′) and an R^(b′) attached to the same carbon are taken together toform a bicyclic carbocycle comprising two optionally substituted5-7-membered carbocyclic rings.

In certain embodiments, an R^(a′) and an R^(b′) attached to the samecarbon are taken together to form an optionally substituted3-12-membered carbocyclic ring. In certain embodiments, an R^(a′) and anR^(b′) attached to the same carbon are taken together to form anoptionally substituted 3-8-membered carbocyclic ring. In certainembodiments, an R^(a′) and an R^(b′) attached to the same carbon aretaken together to form an optionally substituted 5-7-memberedcarbocyclic ring.

In some embodiments, an R^(b′) and an R^(c′) attached to adjacentcarbons are taken together to form one or more optionally substituted3-12-membered carbocyclic rings. In some embodiments, an R^(b′) and anR^(c′) attached to adjacent carbons are taken together to form apolycyclic carbocycle comprising two or more optionally substituted3-8-membered carbocyclic rings. In some embodiments, an R^(b′) and anR^(c′) attached to adjacent carbons are taken together to form apolycyclic carbocycle comprising two or more optionally substituted5-7-membered carbocyclic rings.

In some embodiments, an R^(b′) and an R^(c′) attached to adjacentcarbons are taken together to form a bicyclic carbocycle comprising twooptionally substituted 3-12-membered carbocyclic rings. In someembodiments, an R^(b′) and an R^(c′) attached to adjacent carbons aretaken together to form a bicyclic carbocycle comprising two optionallysubstituted 3-8-membered carbocyclic rings. In some embodiments, anR^(b′) and an R^(c′) attached to adjacent carbons are taken together toform a bicyclic carbocycle comprising two optionally substituted5-7-membered carbocyclic rings.

In certain embodiments, an R^(b′) and an R^(c′) attached to adjacentcarbons are taken together to form an optionally substituted3-12-membered carbocyclic ring. In certain embodiments, an R^(b′) and anR^(c′) attached to adjacent carbons are taken together to form anoptionally substituted 3-8-membered carbocyclic ring. In certainembodiments, an R^(b′) and an R^(c′) attached to adjacent carbons aretaken together to form an optionally substituted 5-7-memberedcarbocyclic ring.

In certain embodiments, the polymer comprises a copolymer of twodifferent repeating units where R^(a′), R^(b′), and R^(c′) of the twodifferent repeating units are not all the same. In some embodiments, apolymer comprises a copolymer of three or more different repeating unitswherein R^(a′), R^(b′), and R^(c′) of each of the different repeatingunits are not all the same as R^(a′), R^(b′), and R^(c′) of any of theother different repeating units. In some embodiments, a polymer is arandom copolymer. In some embodiments, a polymer is a tapered copolymer.

In some embodiments, a polymer contains a metal complex as describedherein. In some embodiments, a polymer comprises residue of a metalcomplex as described herein. In some embodiments, a polymer comprises asalt of an organic cation and X, wherein X is a nucleophile orcounterion. In some embodiments, X is 2,4-dinitrophenolate anion.

In some embodiments, R^(a′) is optionally substituted C₁₋₁₂ aliphatic.In some embodiments, R^(a′) is optionally substituted C₁₋₁₂heteroaliphatic. In some embodiments, R^(a′) is optionally substitutedphenyl. In some embodiments, R^(a′) is optionally substituted 8- to10-membered aryl. In some embodiments, R^(a′) is optionally substituted5- to 10-membered heteroaryl. In some embodiments, R^(a′) is optionallysubstituted 3- to 7-membered heterocyclic.

In certain embodiments, R^(a′) is selected from methyl, ethyl, propyl,butyl, vinyl, allyl, phenyl, trifluoromethyl,

or any two or more of the above. In certain embodiments, R^(a′) ismethyl. In certain embodiments, R^(a′) is ethyl. In certain embodiments,R^(a′) is propyl. In certain embodiments, R^(a′) is butyl. In certainembodiments, R^(a′) is vinyl. In certain embodiments, R^(a′) is allyl.In certain embodiments, R^(a′) is phenyl. In certain embodiments, R^(a′)is trifluoromethyl. In certain embodiments, R^(a′) is

In certain embodiments, R^(a′) is

In certain embodiments, R^(a′) is

In certain embodiments, R^(a′) is

In certain embodiments,R^(a′) is

In certain embodiments, R^(a′)

In certain embodiments, R^(a′) is

In some embodiments, R^(b′) is hydrogen. In some embodiments, R^(b′) isoptionally substituted C₁₋₁₂ aliphatic. In some embodiments, R^(b′) isoptionally substituted C₁₋₁₂ heteroaliphatic. In some embodiments,R^(b′) is optionally substituted phenyl. In some embodiments, R^(b′) isoptionally substituted 8- to 10-membered aryl. In some embodiments,R^(b′) is optionally substituted 5- to 10-membered heteroaryl. In someembodiments, R^(b′) is optionally substituted 3- to 7-memberedheterocyclic.

In some embodiments, R^(c′) is hydrogen. In some embodiments, R^(c′) isoptionally substituted C₁₋₁₂ aliphatic. In some embodiments, R^(c′) isoptionally substituted C₁₋₁₂ heteroaliphatic. In some embodiments,R^(c′) is optionally substituted phenyl. In some embodiments, R^(c′) isoptionally substituted 8- to 10-membered aryl. In some embodiments,R^(c′) is optionally substituted 5- to 10-membered heteroaryl. In someembodiments, R^(c′) is optionally substituted 3- to 7-memberedheterocyclic.

In some embodiments, R^(a′) and R^(c′) are taken together withintervening atoms to form one or more rings selected from the groupconsisting of: optionally substituted C₃₋C₁₄ carbocycle, optionallysubstituted 3- to 14-membered heterocycle, optionally substitutedphenyl, optionally substituted C₈-C₁₀ aryl, and optionally substituted5- to 10-membered heteroaryl.

In some embodiments, R^(b′) and R^(c′) are taken together withintervening atoms to form one or more rings selected from the groupconsisting of: optionally substituted C₃₋C₁₄ carbocycle, optionallysubstituted 3- to 14-membered heterocycle, optionally substitutedphenyl, optionally substituted C₈₋C₁₀ aryl, and optionally substituted5- to 10-membered heteroaryl.

In some embodiments, R^(a′) and R^(b′) are taken together withintervening atoms to form one or more rings selected from the groupconsisting of: optionally substituted C₃₋C₁₄ carbocycle, optionallysubstituted 3- to 14-membered heterocycle, optionally substitutedphenyl, optionally substituted C₈₋C₁₀ aryl, and optionally substituted5- to 10-membered heteroaryl.

In some embodiments, the invention includes methods for synthesizingpolyethers from epoxides. Suitable methods of performing these reactionsare disclosed in U.S. Pat. No. 7,399,822, the entire contents of whichare hereby incorporated herein by reference.

In some embodiments, the invention includes methods for synthesizingcyclic carbonates from carbon dioxide and epoxides using catalystsdescribed above, suitable methods of performing this reaction aredisclosed in U.S. Pat. No. 6,870,004 which is incorporated herein byreference.

EXAMPLES Example 1

A general route to a symmetric cobalt (III) salen ligand of the presentinvention is shown in Schemes E1 and E2, below:

As shown in Scheme E1, disubstituted phenol E1-a is formylated toprovide salicylaldehyde derivative E1-b. Two equivalents of thisaldehyde are then reacted with a diamine (in this case 1,2-diaminocyclohexane) to afford Schiff base E1-c. This compound is then reactedwith cobalt (II) acetate to give the Co(II)-salen complex (not shown)which is oxidized by air in the presence of trifluoroacetic acid toafford the active cobalt (III) catalyst. Similar chemistries can beapplied to synthesis of the catalysts described hereinabove. One skilledin the art of organic synthesis can adapt this chemistry as needed toprovide the specific catalysts described herein.

Example 2

A typical route to an asymmetric cobalt (III) salen ligand is shown inScheme E2:

As shown in Scheme E2, disubstituted salicylaldehyde derivative E1-b istreated with one equivalent of a monohydrochloride salt of 1,2cyclohexanediamine. the resulting Schiff base E2-a is then neutralizedand a second different salicylaldehyde derivative is added. Thiscompound is then reacted with cobalt (II) acetate to give theCo(II)-salen complex which is oxidized by air in the presence oftrifluoroacetic acid to afford the active cobalt (III) catalyst. Similarchemistries can be applied to synthesis of the catalysts describedhereinabove. One skilled in the art of organic synthesis can adapt thischemistry as needed to provide the specific catalysts described herein.

Example 3

Example 3 describes the synthesis of a catalyst

where M is Co(II),

is salcy,

is

Z is a P-linked phosphorimine moiety

and m is 1, wherein there are one or two

(Z)_(m) groups present (Scheme E4 and E3, respectively).

As shown in Scheme E3, triol E3-a is protected as a ketal to affordmonohydric alcohol E3-b, this compound is then alkylated with bromideE3-c to afford benzyl ether E3-d. Deprotection and oxidation of theother benzylic alcohol affords salicylaldehyde E3-e which is condensedwith cyclohexanediamine as described above to give ligand E3-f. Thephosphorimine nitrogen is then quaternized and the metal complex formedas before to provide catalyst E3-h. In an alternative route not shownhere the metal is first inserted and then quaternization is performed.

As shown in Scheme E3b, salicyladedyde E3-e (described above) iscondensed with cyclohexanediamine monohydrochloride to afford themono-Schiff base hydrochloride E4a. This salt is then neutralized,condensed with di-t-butyl salicaldehyde, and methylated to give E4-b.The resulting ligand is metallated and oxidized as described above forScheme E3 to give catalyst E4-c.

Example 4

Example 4 describes the synthesis of catalysts where M is Co(III),

is salcy,

is

Z is a 1-[4-dimethylamino-pyridinium]

or 1-[N-methylimidazolium],

and m is 1, wherein there are one or two

(Z)_(m) groups present (Scheme E5 and E6, respectively).

Scheme E4 shows the synthesis of compounds CS-6 and CS-7. For eachcompound trans-1,2-Diaminocyclohexane (2.0 mol) is slowly added to ananhydrous ethanol solution of benzyl chloride CS-4 (1.0 mol). Thereaction is stirred and heated to reflux for 3 h, then cooled to rt anddiluted with water. This mixture is cooled overnight in the freezer andsolids are collected by filtration to afford dichloride CS-5. Thedichloride CS-5 (1.0 mol) is reacted with N,N-Dimethylamino pyridine(2.0 mol) or N-methyl imidazole in acetonitrile. The reactions areheated at 80° C. for 18 h and then the solvent is removed in vacuo toprovide the respective ammonium salts. These salts are metallated andoxidized as described previously to provide catalysts CS-6 and CS-7.

Example 5

Example 5 describes the synthesis of catalysts where M is Co(III),

is salcy,

is

Z is a 1-[N-methylimidazolium] (CS-8), or dimethylamino (CS-9) and m is1, wherein there are two

(Z)_(m) groups present (Scheme E5 and E6, respectively).

Scheme E5 shows the synthesis of compounds CS-8 and CS-9 usingconditions similar to those described above. Synthesis of CS-8: Theknown compound 1-(2-methylaminoethyl)-3-methylimidazole (2.0 mol) iscombined with CS-5 (1.0 mol) in acetonitrile. The reaction is heated to80° C. for 18 h and then the solvent is removed in vacuo, metallationwith Co(OAc)₂ and oxidation in TFA are then performed as described aboveto afford catalyst CS-8. Synthesis of CS-9:N,N,N′-Trimethyl-1,2-ethanediamine (4.0 mol) is combined with CS-5 (1.0mol) in acetonitrile. The reaction is heated to 80° C. for 18 h, cooled,and the solvent is removed in vacuo. The crude product is diluted withether, filtered to remove amine salts, and concentrated in vacuo. Theresidue is dissolved in degassed methanol and combined with Co(OAc)₂(1.0 mol). After stirring for 3 h the residue is filtered and washedwith methanol. Trifluoroacetic acid (1.0 mol) is added slowly to astirring solution of the solid residue in dichloromethane. Afterstirring open to air for 3 h, the solids are filtered and dried in vacuoto produce CS-9.

Example 6

Example 6 and Scheme E6 describe the synthesis of catalysts where M isCo(III),

is salcy,

is

Z is dibutylamino and in is 1, wherein there are two

(Z)_(m) groups present.

Synthesis of CS-10:

Ligand CS-5 (1.0 mol), 3-(dibutylamino)-1-propanol (2.0 mol), a 50% NaOHsolution (10 mol), tetrabutylammonium bisulphate (4 mol %), anddichloromethane are combined and heated at 65° C. overnight. Thereaction mixture is concentrated in vacuo to remove the bulk of thesolvent and the aqueous layer is extracted with ethyl acetate. Theorganic layer is separated, dried with magnesium sulfate, filtered, andconcentrated in vacuo. After purification using silica gel the productis dissolved in degassed methanol and combined with Co(OAc)₂ (1.0 mol).After stirring for 3 h, the residue is filtered and washed withmethanol. Trifluoroacetic acid (1.0 mol) is added slowly to adichloromethane solution of the solid residue. After stirring open toair for 3 h, the solids are filtered and dried in vacuo to produceCS-10.

Example 7

Example 7 and Scheme E7 describe the synthesis of catalysts where M isCo(III),

is salcy,

includes two

groups taken together to form a ring including the Z group, Z is3-[N-methylpyridinium] and m is 1, wherein there is one

(Z)_(m) group present.

Synthesis of CS-11.

Ligand CS-5 (1.0 mol), 3,5-bis(hydroxymethyl)-N-methylpyridinium iodide(2.0 mol), a 50% NaOH solution (10 mol), tetrabutylammonium bisulphate(4 mol %), and dichloromethane are combined and heated at 65° C.overnight. The reaction mixture is concentrated in vacuo to remove thebulk of the solvent and the aqueous layer is extracted with ethylacetate. The organic layer is separated, dried with magnesium sulfate,filtered, and concentrated in vacuo. The procedure detailed above forthe metallation and oxidation is followed to produce CS-11.

Example 8

Example 8 and Scheme E8 describe the synthesis of catalysts where M isCo(III),

is salcy,

is

Z is 1-[4-t-butylpyridinium], and m is 2, wherein there are two

(Z)_(m) groups present.

Synthesis of AC-2.

Intermediate AC-1 (0.37 g, 0.35 mmol), 4-tbutylpyridine (0.21 mL, 1.41mmol), and AcCN (4 mL) were combined in a sealed vial and heated to 80°C. with stirring for 18 h. The solvent was removed in vacuo, leaving ayellow residue (0.61 g, 110% yield, AcCN present). ¹H NMR (400 MHz,CDCl₃, δ): 9.53 (t, 8H), 8.21 (s, 2H), 7.94 (t, 8H), 7.08 (s, 2H), 6.83(s, 2H), 4.81 (m, 8H), 3.29 (m, 2H), 2.78 (m, 2H), 2.15 (s, 6H), 1.5-2.0(m, 24H), 1.36 (s, 36H); IR (ATR, film cast from AcCN): ν_(C═N)=1637cm⁻¹. A solution of the residue (0.30 g, 0.19 mmol) in dry EtOH (5 mL)was added to AgBF₄ (0.19 g, 0.85 mmol) in a schlenk tube and stirredovernight shielded from the light. The solution was filtered throughCelite and the solvent was removed in vacuo, giving a solid residue.This residue was flashed over a small plug of silica gel with 5:1CH₂Cl₂:EtOH as eluant. The solvent was removed to give a solid residue(0.18 g, 67% yield). ¹H NMR (400 MHz, CDCl₃, δ): 8.75 (t, 8H), 7.98 (d,2H), 7.92 (t, 8H), 7.1-7.3 (m, 4H), 4.52 (m, 8H), 3.6 (m, 2H), 2.7 (m,2H), 2.19 (s, 6H), 1.5-2.0 (m, 24H), 1.38 (s, 36H); IR (ATR, film castfrom CH₂Cl₂): ν_(C═N)=1641 cm⁻¹, ν_(BF) ₄ =1050 cm⁻¹. A solution of theresidue (0.18 g, 0.12 mmol) in dry EtOH (4 mL) was added to Co(OAc)₂(0.022 g, 0.12 mmol) in a schlenk tube under N₂. The solution wasstirred for 3 h at room temperature, and the solvent was removed invacuo. The residue was triturated with ether, dried in vacuo, andredissolved in CH₂Cl₂. A solution of CF₃CO₂H (9 μL, 0.12 mmol) in CH₂Cl₂(80 μL) was added and the solution stirred for 3 h open to air. SolidNaO₂CCF₃ (0.067 g, 0.49 mmol) was added, and the solution was stirredunder N₂ for 2 days. The solution was filtered through Celite and thesolvent was removed in vacuo to leave a brown residue (0.071 g, 37%yield). ¹H NMR (400 MHz, DMSO-d₆, δ): 8.86 (t, 8H), 8.08 (t, 8H), 8.07(s, 2H), 7.30 (m, 4H), 4.44 (m, 8H), 3.54 (m, 2H), 2.9 (m, 2H), 2.47 (s,6H), 1.5-2.0 (m, 24H), 1.29 (s, 36H); IR (ATR): ν_(C═O)=1682 cm⁻¹,ν_(C═N)=1641 cm⁻¹.

Additional ligands AC-6 through AC-11 were synthesized using theconditions described for compound AC-2 and are summarized in Scheme E8band Table E8:

TABLE E8 Scheme E8b

Q Compound (Scheme E8b) ¹H NMR spectra^(a) (δ, ppm) IR^(b) (cm⁻¹)AC-6^(c)

9.0 (d, 8H), 8.6 (t, 4H), 8.5 (s, 2H), 8.1 (t, 8H), 6.9 (s, 2H), 6.8 (s,2H), 4.5 (t, 8H), 3.4 (m, 2H), 2.1 (s, 6H), 1.4-2.9 (m, 24H). ν_(C═N) =1629 AC-7

8.61 (d, 8H), 8.29 (s, 2H), 6.99 (s, 2H), 6.92 (d, 8H), 6.85 (s, 2H),4.30 (t, 8H), 3.34 (m, 2H), 3.23 (s, 24H), 2.65 (m, 2H), 2.18 (s, 6H),1.4-2.9 (m, 16H). ν_(C═N) = 1649 AC-8

ν_(C═N) = 1627 AC-9

ν_(C═N) = 1610 AC-10

ν_(C═N) = 1627 AC-11

ν_(C═N) = 1628 ^(α)400 MHz, CDCl₃. ^(b)All compounds exhibited the lossof a peak at 1213 cm⁻¹ attributed to the CH₂I group in AC-1. ^(c)NMRspectrum is in DMSO-d₆.

Example 9

Example 9 and Scheme E9 describe the synthesis of catalysts where M isCo(III),

is salcy,

is

Z is N,N-bis-(3-dimethylaminopropyl)amino (AC-4), tetramethyl guanidino(AC-5), N-linked morpholino (AC-6), or N-linked piperidino (AC-14), andm is 2, wherein there are two

(Z)_(m) groups present.

Synthesis of AC-4.

Intermediate AC-3 (0.45 g, 0.63 mmol),3,3′-iminobis(N,N′-dimethylpropylamine) (0.28 mL, 1.26 mmol), K₂CO₃(0.35 g, 2.52 mmol) and AcCN (5 mL) were combined in a sealed vial andheated to 80° C. with stirring for 18 h. The solution was filtered andthe solvent was removed in vacuo, triturated with ether, and dried invacuo to leave a yellow residue (0.48 g, 91% yield). ¹H NMR (400 MHz,CDCl₃, δ): 8.21 (m, 2H), 6.8-7.2 (m, 4H), 3.75 (m, 2H), 3.0-3.4 (m,20H), 2.0-2.8 (m, 28H), 2.18 (s, 6H), 1.4-2.0 (m, 24H); IR (ATR):ν_(C═N)=1600 cm⁻¹. A solution of the residue (0.21 g, 0.25 mmol) in dryEtOH (10 mL) was added to Co(OAc)₂ (0.045 g, 0.25 mmol) in a schlenktube under N₂. CH₂Cl₂ (3 mL) was added to completely dissolve thesolution. The solution was stirred for 18 h at room temperature, and thesolvent was removed in vacuo. The residue was triturated with ether,dried in vacuo, and redissolved in CH₂Cl₂ (10 mL). CF₃CO₂H (20 μL, 0.25mmol) was added and the solution stirred for 3.5 h open to air. Thesolvent was removed in vacuo, triturated with ether, and dried in vacuoto leave a brown residue (0.28 g, 108% yield, residual CH₂Cl₂). ¹H NMR(400 MHz, DMSO-d₆, δ): 7.92 (m, 2H), 7.1-7.4 (m, 4H), 3.58 (m, 2H),3.0-3.4 (m, 20H), 2.0-2.8 (m, 28H), 2.3 (s, 6H), 1.4-2.0 (m, 24H); IR(ATR): ν_(C═O)=1688 cm⁻¹, ν_(C═N)=1616 cm¹.

Synthesis of AC-5.

Intermediate AC-3 (0.20 g, 0.29 mmol), 1,1,3,3-tetramethylguanidine(0.21 mL, 1.71 mmol), K₂CO₃ (0.39 g, 2.85 mmol) and AcCN (2 mL) werecombined in a sealed vial and reacted as in AC-4, except that theresidue was also washed with hexanes. ¹H NMR (400 MHz, CDCl₃, δ): 8.23(d, 2H), 6.95 (s, 2H), 6.80 (s, 2H), 3.35 (m, 2H), 3.1 (m, 4H), 2.7-2.8(m, 24H), 2.48 (m, 4H), 2.20 (s, 6H), 1.4-2.0 (m, 16H); IR (ATR):ν_(C═N)=1594 cm⁻¹. The residue was reacted as in AC-4. TR (ATR):ν_(C═O)=1690 cm⁻¹, ν_(C═N)=1610 cm¹.

Synthesis of AC-6.

Intermediate AC-3 (0.32 g, 0.44 mmol), morpholine (0.16 mL, 1.77 mmol),K₂CO₃ (0.61 g, 4.4 mmol) and AcCN (4 mL) were combined in a sealed vialand reacted as in AC-4, except that the residue was also washed with aNaOAc buffer (pH=4) solution to remove residual morpholine. ¹H NMR (400MHz, CDCl₃, δ): 8.22 (s, 2H), 6.92 (s, 2H), 6.79 (s, 2H), 3.69 (m, 8H),3.28 (m, 2H), 2.2-2.5 (m, 16H), 2.19 (s, 6H), 1.4-2.0 (m, 16H). Theresidue was reacted as in AC-4. ¹H NMR (400 MHz, DMSO-d₆, δ): 7.91 (s,2H), 7.23 (s, 2H), 7.14 (s, 2H), 3.6 (m, 2H), 3.52 (m, 8H), 2.99 (m,2H), 2.57 (s, 6H), 2.47 (m, 4H), 2.2-2.5 (m, 12H), 1.4-2.0 (m, 16H); IR(ATR): ν_(C═O)=1671 cm⁻¹, ν_(C═N)=1630 cm⁻¹.

Additional ligands AC-13 and AC-14 were synthesized using the conditionsdescribed for compounds AC-4 through AC-6 and are summarized in SchemeE9b and Table E9:

TABLE E9 Q Compound (Scheme E9b) ¹H NMR spectra^(α) (δ, ppm) IR^(b)(cm⁻¹) AC-13

8.25 (s, 2H), 7.02 (d, 2H), 6.77 (d, 2H), 3.7 (m, 8H), 3.3 (m, 2H),2.2-2.6 (m, 12H), 1.3-2.0 (m, 20H), 1.37 (s, 18H) ν_(C═N) = 1628 AC-14

ν_(C═N) = 1629 ^(α)400 MHz, CDCl₃. ^(b)All compounds exhibited the lossof a peak at 1213 cm⁻¹ attributed to the CH₂I group in AC-1.

Example 10

Confirmation of inventive concepts, processes, methods, and compositionsdescribed herein has been provided, among other ways, throughpublication by others after the priority date of the present case. Forexample, Examples 10-27 describe working Examples presented in ChinesePatent Application No. 200810229276.1, published as CN 101412809A.Additional experimental and characterization data are described by Luand co-workers, J. Am. Chem. Soc., 2009, 131, 11509-11518, andsupporting information available at www.pubs.acs.org, the entirety eachof which is hereby incorporated by reference.

In certain embodiments, provided catalysts and/or methods for thepreparation of polycarbonate are characterized by one or more of thefollowing: retaining high catalytic activity at low catalystconcentration; reaction conditions that are relatively mild; highcatalytic activity with high selectivity for polymer product; alternatestructure in the polycarbonate product higher than 97% with relativelynarrow distribution of molecular weight; retaining high catalyticactivity for copolymerization of carbon dioxide and epoxides at higherreaction temperatures (e.g., above 50° C., above 75° C., or above 100°C.); and catalysts that can be used to catalyze the polymerization ofcarbon dioxide with two or more alkylene oxides for the synthesis ofpolycarbonate polymer.

The following materials were added sequentially into a stainless steelhigh pressure reactor of effective volume of 200 mL at ambienttemperature: 0.1 mmole of cobalt complex I-a (R₁ is cyclohexyl diamine,X is NO₃ ⁻¹ anion; R₂═H; R₃, R₄ and R₅ are tertiary butyl; groupcontaining organic base group is at position 3 of the benzene ring inthe ligand, n is 2) and one mole of propylene oxide. The reactor wasthen filled with carbon dioxide and the pressure is maintained constantat 2.0 MPa. The temperature was controlled at 25° C. The content wasstirred with a magnetic stirring bar for 6 hours and the remainingcarbon dioxide was slowly released. The remaining alkylene oxide wascollected in −20° C. cold trap and a certain amount of mixture ofmethanol/chloroform was added to dissolve the high polymer. Then a largeamount of diethyl ether was added to precipitate the polycarbonate. Theprecipitate was filtered and washed several times with diethyl ether anddried in vacuum to constant weight to afford 27 grams of polycarbonateas a white solid. The average molecular weight of the polymer wasdetermined by gel permeation chromatography to be 101,000 g/mol with amolecular weight distribution of 1.24. A Varian INOVA-400 MHz NuclearMagnetic Resonance spectrometer was used to determine its ¹H-NMR and theresult showed that the alternate structure is over 99%.

Example 11

The same equipment and reaction conditions were employed as in Example10 with the same catalyst and the same conditions except that the molarratio of catalyst to propylene oxide was changed from 1:10000 to 1:50000(0.02 mmole of catalyst and 1 mole of propylene oxide were used). Thereaction was carried out at 25° C. for 24 hours to afford 21 grams ofpoly(propylene carbonate) with a molecular weight of 223,000 g/mol and amolecular weight distribution of 1.29. The polymer formed contained morethan 99% carbonate linkages.

Example 12

The same equipment and reaction conditions were employed as in Example10 with the same catalyst and the same conditions except that the molarratio of catalyst to propylene oxide was changed from 1:10000 to1:200000 (0.008 mmole of catalyst and 1.6 mole of propylene oxide wereused). The reaction was carried out at 50° C. for 10 hours to afford 19grams of poly(propylene carbonate) with a molecular weight of 318,000g/mol and a molecular weight distribution of 1.37. The polymer formedcontained more than 99% carbonate linkages.

Example 13

The same equipment and reaction conditions were employed as in Example10 with the same catalyst and the same conditions except that the molarratio of catalyst to propylene oxide was changed from 1:10000 to 1:2000(0.5 mmole of catalyst and 1 mole of propylene oxide were used). Thereaction was carried out at 25° C. for 3 hours to afford 48 grams ofpoly(propylene carbonate) with a molecular weight of 52,800 g/mol and amolecular weight distribution of 1.30. The polymer formed contained morethan 99% carbonate linkages.

Example 14

The same equipment and reaction conditions were employed as in Example10 with the same catalyst and the same conditions except that thereaction temperature was changed from 25° C. to 100° C. and the reactionwas carried out for 0.5 hours to afford 34 grams of poly(propylenecarbonate) with a molecular weight of 112,400 g/mol and a molecularweight distribution of 1.38. The polymer formed contained more than 99%carbonate linkages.

Example 15

The same equipment and reaction conditions were employed as in Example10 with the same catalyst and the same conditions except that thereaction temperature was changed from 25° C. to 10° C. and the reactionwas carried out for 10 hours to afford 18 grams of poly(propylenecarbonate) with a molecular weight of 914,000 g/mol and a molecularweight distribution of 1.38. The polymer formed contained more than 99%carbonate linkages.

Example 16

The same equipment and reaction conditions were employed as in Example10 with the same catalyst and the same conditions except that thepropylene oxide was replaced with 1,2-butylene oxide. The reaction wascarried out at 25° C. for 6 hours to afford 31 grams of poly(butylenecarbonate) with a molecular weight of 127,000 g/mol and a molecularweight distribution of 1.21. The polymer formed contained more than 99%carbonate linkages.

Example 17

The same equipment and reaction conditions were employed as in Example10 with the same catalyst and the same conditions except that thepropylene oxide was replaced with 1,2-octylene oxide. The reaction wascarried out at 25° C. for 10 hours to afford 34 grams of poly(octylenecarbonate) with a molecular weight of 109,000 g/mol and a molecularweight distribution of 1.38. The polymer formed contained more than 99%carbonate linkages.

Example 18

The same equipment and reaction conditions were employed as in Example10 with the same catalyst and the same conditions except that thepropylene oxide was replaced with a mixture of propylene oxide andcyclohexylene oxide (the molar ratio of the catalyst to propylene oxideand cyclohexylene oxide was 1:5000:5000). The reaction was carried outat 50° C. for 6 hours to afford 59 grams ofpoly(propylene-co-cylcohexene carbonate) with a molecular weight of187,000 g/mol and a molecular weight distribution of 1.29. The polymerformed contained more than 99% carbonate linkages.

Example 19

The same equipment and reaction conditions were employed as in Example10 with the same catalyst and the same conditions except that the axialanion in the cobalt complex I-a was changed from nitrate radical toacetate moiety. The reaction was carried out at 25° C. for 6 hours toafford 34 grams of poly(propylene carbonate) with a molecular weight of95,000 g/mol and a molecular weight distribution of 1.28. The polymerformed contained more than 99% carbonate linkages.

Example 20

The same equipment and reaction conditions were employed as in Example10 with the same catalyst and the same conditions except that thediamine skeleton in the cobalt complex I-a was changed from cyclohexanediamine to ethylene diamine. The reaction was carried out at 25° C. for6 hours to afford 29 grams of poly(propylene carbonate) with a molecularweight of 112,000 g/mol and a molecular weight distribution of 1.20. Thepolymer formed contained more than 99% carbonate linkages.

Example 21

The same equipment and reaction conditions were employed as in Example10 with the same catalyst and the same conditions except that thediamine skeleton in the cobalt complex I-a was changed from cyclohexanediamine to o-phenylene diamine. The reaction was carried out at 25° C.for 6 hours to afford 25 grams of poly (propylene carbonate) with amolecular weight of 92,000 g/mol and a molecular weight distribution of1.15. The polymer formed contained more than 99% carbonate linkages.

Example 22

The following materials were added sequentially into a stainless steelhigh pressure reactor of volume of 200 mL at ambient temperature: 0.1mmole of cobalt complex 1-b (R₁ is 1,2-propylene diamine, X isdinitrophenyl anion; R₂═H; R₁ is tertiary butyl; there are organic basegroups at position 5 of the two benzene rings in the ligand, n is 0) and1 mole of propylene oxide. The reactor was then filled with carbondioxide and the pressure was maintained constant at 2.0 MPa. Thereaction was carried out at 25° C. for 6 hours to afford 23 grams ofpolycarbonate as a white solid. The average molecular weight of thepolymer was determined by gel permeation chromatography to be 81,000g/mol with a molecular weight distribution of 1.34. The polymer formedcontained more than 99% carbonate linkages.

Example 23

The following materials were added sequentially into a stainless steelhigh pressure reactor of volume of 200 mL at ambient temperature: 0.1mmole of cobalt complex I-c (R₁ is ethylene diamine, X is dinitrophenylanion; R₂═H; R₃ is tertiary butyl; there are organic base groups atposition 3 and position 5 of one of the benzene rings in the ligand, nis 0) and 1 mole of propylene oxide. The reactor was then filled withcarbon dioxide and the pressure was maintained constant at 2.0 MPa. Thereaction was carried out at 25° C. for 6 hours to afford 23 grams ofpolycarbonate as a white solid. The average molecular weight of thepolymer was determined by gel permeation chromatography to be 81,000g/mol with a molecular weight distribution of 1.34. The polymer formedcontained more than 99% carbonate linkages.

Example 24

The following materials are added sequentially into a stainless steelhigh pressure reactor of volume of 200 mL at ambient temperature: 0.1mmole of cobalt complex I-b (R₁ is ethylene diamine, X is dinitrophenylanion; R₂═H; R₃ and R₄ are tertiary butyl; there are organic base groupsat position 5 of the two benzene rings in the ligand, n is 0) and 1 moleof propylene oxide. The reactor was then filled with carbon dioxide andthe pressure was maintained constant at 2.0 MPa. The reaction wascarried out at 25° C. for 6 hours to afford 26 grams of polycarbonate asa white solid. The average molecular weight of the polymer wasdetermined by gel permeation chromatography to be 83,000 g/mol with amolecular weight distribution of 1.19. The polymer formed contained morethan 99% carbonate linkages. The polymer formed contained more than 99%carbonate linkages.

Example 25

The following materials are added sequentially onto a stainless steelhigh pressure reactor of volume of 200 mL at ambient temperature: 0.1mmole of cobalt complex I-a (R₁ is 2,3-butylene diamine, X is nitrateanion; R₂═H; R₃ and R₄ are methoxyl group; R₁ is tertiary butyl; thereis an organic base group at position 3 of one of the benzene rings inthe ligand, n is 2) and 1 mole of propylene oxide. The reactor was thenfilled with carbon dioxide and the pressure is maintained constant at2.0 MPa. The reaction was carried out at 25° C. for 6 hours to afford 22grams of polycarbonate as a white solid. The average molecular weight ofthe polymer was determined by gel permeation chromatography to be 73,000g/mol with a molecular weight distribution of 1.14. The polymer formedcontained more than 99% carbonate linkages.

Example 26

The same equipment and reaction conditions were employed as in Example10 with the same catalyst and the same conditions except that thepressure was changed from 2.0 MPa to 0.1 MPa. The reaction was carriedout at 25° C. for 10 hours to afford 25 grams of poly(propylenecarbonate) with a molecular weight of 100,400 g/mol and a molecularweight distribution of 1.17. The polymer formed contained more than 99%carbonate linkages.

Example 27

The same equipment and reaction conditions were employed as in Example10 with the same catalyst and the same conditions except that thepressure was changed from 2.0 MPa to 6.0 MPa. The reaction was carriedout at 25° C. for 6 hours to afford 29 grams of poly(propylenecarbonate) with a molecular weight of 125,000 g/mol and a molecularweight distribution of 1.25. The polymer formed contained more than 99%carbonate linkages.

TABLE E10 Summary of Examples 10-27. Reaction Conditions Catalyst Cat.Epoxide P T t Ex Cat R1 R2 R3 R4 R5 X n (mmol) (mg) (mmol) MPa psi (degC.) (h) 10 I-a Cy H tBu tBu tBu NO₃ 2 PO 0.1 70.5 1000 2 290 25 6 110.02 14.1 1000 2 290 25 24 12 0.008 5.64 1600 2 290 50 10 13 0.5 3531000 2 290 25 3 14 0.1 70.5 1000 2 290 100 0.5 15 0.1 70.5 1000 2 290 1010 26 0.1 70.5 1000 0.1 15 25 10 27 0.1 70.5 1000 6 870 25 6 16 BO 0.170.5 1000 2 290 25 6 17 OO 0.1 70.5 1000 2 290 25 10 18 PO/CHO 0.1 70.51000 2 290 50 6 19 Cy H tBu tBu tBu OAc 2 PO 0.1 70.2 1000 2 250 25 6 20En H tBu tBu tBu NO₃ 2 PO 0.1 65.1 1000 2 290 25 6 21 Ph H tBu tBu tBuNO₃ 2 PO 0.1 69.9 1000 2 290 25 6 25 Bu H OMe OMe tBu NO₃ 2 PO 0.1 62.71000 2 290 25 6 22 I-b Pr tBu DNP 0 PO 0.1 89 1000 2 290 25 6 24 I-b EnH tBu DNP 0 PO 0.1 87.7 1000 2 290 25 6 23 I-c En H tBu tBu DNP 0 PO 0.188.2 1000 2 290 25 6 Results Catalyst PPC TOF MW g PC/ kg PC/ Ex Cat R1R2 R3 R4 R5 X n yield (g) conv. (%) TON (h⁻¹) (kDa) PDI g Cat mol Cat.10 I-a Cy H tBu tBu tBu NO₃ 2 27 26.4 2644 441 101 1.2 383 270 11 2120.6 10284 429 233 1.3 1489 1050 12 19 11.6 23262 2326 318 1.4 3369 237513 48 47.0 940 313 53 1.3 136 96 14 34 33 3330 6660 112 1.4 482 340 1518 17.6 1763 176 914 1.4 255 180 26 25 24.5 2449 244.9 100 1.2 355 25027 29 28.4 2840 473.4 125 1.3 411 290 16 31 26.7 2669 444.9 127 1.2 440310 17 34 19.7 1974 197.4 109 1.4 482 340 18 59 837 590 19 Cy H tBu tButBu OAc 2 34 33.3 3330 555 95 1.3 484 340 20 En H tBu tBu tBu NO₃ 2 2928.4 2840 473 112 1.2 446 290 21 Ph H tBu tBu tBu NO₃ 2 25 24.5 2449 40892 1.2 358 250 25 Bu H OMe OMe tBu NO₃ 2 22 21.5 2155 359.1 73 1.1 351220 22 I-b Pr tBu DNP 0 23 22.5 2253 375 81 1.3 258 230 24 I-b En H tBuDNP 0 26 25.5 2547 424.4 83 1.2 296 260 23 I-c En H tBu tBu DNP 0 2322.5 2253 375.4 81 1.3 261 230

While we have described a number of embodiments of this invention, it isapparent that our basic examples may be altered to provide otherembodiments that utilize the compounds and methods of this invention.Therefore, it will be appreciated that the scope of this invention is tobe defined by the appended claims rather than by the specificembodiments that have been presented by way of example.

What is claimed is:
 1. A metal complex of the formula:

wherein M is a metal atom;

comprises a corrole ligand; and

(Z)_(m) represents one or more activating moieties attached to themultidentate ligand, where

is a linker moiety covalently coupled to the ligand, each Z is anactivating functional group; and m is an integer from 1 to 4representing the number of Z groups present on an individual linkermoiety.
 2. The metal complex of claim 1, wherein

comprises

wherein R^(d) at each occurrence is independently a

(Z)_(m) group, hydrogen, halogen, —OR, —NR₂, —SR, —CN, —NO₂, —SO₂R,—SOR, —SO₂NR₂; —CNO, —NRSO₂R, —NCO, —N₃, —SiR₃; or an optionallysubstituted radical selected from the group consisting of C₁₋₂₀aliphatic; C₁₋₂₀ heteroaliphatic; phenyl; a 3- to 8-membered saturatedor partially unsaturated monocyclic carbocycle; a 7-14 carbon saturated,partially unsaturated or aromatic polycyclic carbocycle; a 5- to6-membered monocyclic heteroaryl ring having 1-4 heteroatomsindependently selected from nitrogen, oxygen, or sulfur; a 3- to8-membered saturated or partially unsaturated heterocyclic ring having1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur;a 6- to 12-membered polycyclic saturated or partially unsaturatedheterocycle having 1-5 heteroatoms independently selected from nitrogen,oxygen, or sulfur; and an 8- to 10-membered bicyclic heteroaryl ringhaving 1-5 heteroatoms independently selected from nitrogen, oxygen, orsulfur; where two or more R^(d) groups may be taken together withintervening atoms to form one or more optionally substituted ringsoptionally containing one or more heteroatoms; and R at each occurrenceis independently hydrogen, an optionally substituted radical selectedthe group consisting of acyl; C₁₋₆ aliphatic; C₁₋₆ heteroaliphatic;carbamoyl; arylalkyl; phenyl; a 3- to 8-membered saturated or partiallyunsaturated monocyclic carbocycle; a 7-14 carbon saturated, partiallyunsaturated or aromatic polycyclic carbocycle; a 5- to 6-memberedmonocyclic heteroaryl ring having 1-4 heteroatoms independently selectedfrom nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated orpartially unsaturated heterocyclic ring having 1-3 heteroatomsindependently selected from nitrogen, oxygen, or sulfur; a 6- to12-membered polycyclic saturated or partially unsaturated heterocyclehaving 1-5 heteroatoms independently selected from nitrogen, oxygen, orsulfur; an 8- to 10-membered bicyclic heteroaryl ring having 1-5heteroatoms independently selected from nitrogen, oxygen, or sulfur; anoxygen protecting group; and a nitrogen protecting group, where two Rgroups on the same nitrogen atom can optionally be taken together toform an optionally substituted 3- to 7-membered ring.
 3. The metalcomplex of claim 2, wherein M is selected from the group consisting ofCr, Mn, V, Fe, Co, Mo, W, Ru, Al, and Ni.
 4. The metal complex of claim2, wherein M is Fe.
 5. The metal complex of claim 2, wherein M is Mn. 6.The metal complex of claim 2, wherein M is Co.
 7. The metal complex ofclaim 2, wherein one or more Z groups is a phosphorous-containingfunctional group independently selected from the group consisting ofphosphines, phosphine oxides, phosphinites, phosphonites, phosphites,

wherein each occurrence of R¹, R², and R³ is independently hydrogen oran optionally substituted radical selected from the group consisting ofC₁₋₂₀ aliphatic; C₁₋₂₀ heteroaliphatic; phenyl; a 3- to 8-memberedsaturated or partially unsaturated monocyclic carbocycle; a 7-14 carbonsaturated, partially unsaturated or aromatic polycyclic carbocycle; a 5-to 6-membered monocyclic heteroaryl ring having 1-4 heteroatomsindependently selected from nitrogen, oxygen, or sulfur; a 3- to8-membered saturated or partially unsaturated heterocyclic ring having1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur;a 6- to 12-membered polycyclic saturated or partially unsaturatedheterocycle having 1-5 heteroatoms independently selected from nitrogen,oxygen, or sulfur; and an 8- to 10-membered bicyclic heteroaryl ringhaving 1-5 heteroatoms independently selected from nitrogen, oxygen, orsulfur; wherein any two or more R¹, R², and R³ groups can be takentogether with intervening atoms to form one or more optionallysubstituted rings optionally containing one or more additionalheteroatoms; each R^(7′) is independently hydrogen, a hydroxylprotecting group, or an optionally substituted radical selected from thegroup consisting of C₁₋₂₀ acyl; C₁₋₂₀ aliphatic; C₁₋₂₀ heteroaliphatic;phenyl; a 3- to 8-membered saturated or partially unsaturated monocycliccarbocycle; a 7-14 carbon saturated, partially unsaturated or aromaticpolycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ringhaving 1-4 heteroatoms independently selected from nitrogen, oxygen, orsulfur; a 3- to 8-membered saturated or partially unsaturatedheterocyclic ring having 1-3 heteroatoms independently selected fromnitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated orpartially unsaturated heterocycle having 1-5 heteroatoms independentlyselected from nitrogen, oxygen, or sulfur; and an 8- to 10-memberedbicyclic heteroaryl ring having 1-5 heteroatoms independently selectedfrom nitrogen, oxygen, or sulfur; wherein two R^(7′) groups can be takentogether with intervening atoms to form an optionally substituted ringoptionally containing one or more heteroatoms; and X is any anion. 8.The metal complex of claim 2, wherein one or more Z groups is a neutralnitrogen containing moiety independently selected from the groupconsisting of

or a combination of two or more of these, wherein: each occurrence of R¹and R² is independently hydrogen or an optionally substituted radicalselected from the group consisting of C₁₋₂₀ aliphatic; C₁₋₂₀heteroaliphatic; phenyl; a 3- to 8-membered saturated or partiallyunsaturated monocyclic carbocycle; a 7-14 carbon saturated, partiallyunsaturated or aromatic polycyclic carbocycle; a 5- to 6-memberedmonocyclic heteroaryl ring having 1-4 heteroatoms independently selectedfrom nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated orpartially unsaturated heterocyclic ring having 1-3 heteroatomsindependently selected from nitrogen, oxygen, or sulfur; a 6- to12-membered polycyclic saturated or partially unsaturated heterocyclehaving 1-5 heteroatoms independently selected from nitrogen, oxygen, orsulfur; and an 8- to 10-membered bicyclic heteroaryl ring having 1-5heteroatoms independently selected from nitrogen, oxygen, or sulfur;wherein two or more R¹ and R² groups can be taken together withintervening atoms to form one or more optionally substituted ringsoptionally containing one or more additional heteroatoms; eachoccurrence of R⁵ is independently hydrogen or an optionally substitutedradical selected from the group consisting of C₁₋₂₀ aliphatic; C₁₋₂₀heteroaliphatic; phenyl; a 3- to 8-membered saturated or partiallyunsaturated monocyclic carbocycle; a 7-14 carbon saturated, partiallyunsaturated or aromatic polycyclic carbocycle; a 5- to 6-memberedmonocyclic heteroaryl ring having 1-4 heteroatoms independently selectedfrom nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated orpartially unsaturated heterocyclic ring having 1-3 heteroatomsindependently selected from nitrogen, oxygen, or sulfur; a 6- to12-membered polycyclic saturated or partially unsaturated heterocyclehaving 1-5 heteroatoms independently selected from nitrogen, oxygen, orsulfur; and an 8- to 10-membered bicyclic heteroaryl ring having 1-5heteroatoms independently selected from nitrogen, oxygen, or sulfur;wherein an R⁵ group can be taken with an R¹ or R² group to form one ormore optionally substituted rings; and each occurrence of R⁷ isindependently hydrogen, a hydroxyl protecting group, or an optionallysubstituted radical selected from the group consisting of C₁₋₂₀ acyl;C₁₋₂₀ aliphatic; C₁₋₂₀ heteroaliphatic; phenyl; a 3- to 8-memberedsaturated or partially unsaturated monocyclic carbocycle; a 7-14 carbonsaturated, partially unsaturated or aromatic polycyclic carbocycle; a 5-to 6-membered monocyclic heteroaryl ring having 1-4 heteroatomsindependently selected from nitrogen, oxygen, or sulfur; a 3- to8-membered saturated or partially unsaturated heterocyclic ring having1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur;a 6- to 12-membered polycyclic saturated or partially unsaturatedheterocycle having 1-5 heteroatoms independently selected from nitrogen,oxygen, or sulfur; and an 8- to 10-membered bicyclic heteroaryl ringhaving 1-5 heteroatoms independently selected from nitrogen, oxygen, orsulfur.
 9. The metal complex of claim 2, wherein one or more Z groups isa cationic moiety independently selected from the group consisting of

or a combination of two or more of these, wherein each occurrence of R¹,R², and R³ is independently hydrogen or an optionally substitutedradical selected from the group consisting of C₁₋₂₀ aliphatic; C₁₋₂₀heteroaliphatic; phenyl; a 3- to 8-membered saturated or partiallyunsaturated monocyclic carbocycle; a 7-14 carbon saturated, partiallyunsaturated or aromatic polycyclic carbocycle; a 5- to 6-memberedmonocyclic heteroaryl ring having 1-4 heteroatoms independently selectedfrom nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated orpartially unsaturated heterocyclic ring having 1-3 heteroatomsindependently selected from nitrogen, oxygen, or sulfur; a 6- to12-membered polycyclic saturated or partially unsaturated heterocyclehaving 1-5 heteroatoms independently selected from nitrogen, oxygen, orsulfur; and an 8- to 10-membered bicyclic heteroaryl ring having 1-5heteroatoms independently selected from nitrogen, oxygen, or sulfur;wherein any two or more R¹, R², and R³ groups can be taken together withintervening atoms to form one or more optionally substituted ringsoptionally containing one or more additional heteroatoms; R^(4′) ishydrogen, hydroxyl, optionally substituted C₁₋₂₀ aliphatic; eachoccurrence of R⁵ and R⁶ is independently hydrogen or an optionallysubstituted radical selected from the group consisting of C₁₋₂₀aliphatic; C₁₋₂₀ heteroaliphatic; phenyl; a 3- to 8-membered saturatedor partially unsaturated monocyclic carbocycle; a 7-14 carbon saturated,partially unsaturated or aromatic polycyclic carbocycle; a 5- to6-membered monocyclic heteroaryl ring having 1-4 heteroatomsindependently selected from nitrogen, oxygen, or sulfur; a 3- to8-membered saturated or partially unsaturated heterocyclic ring having1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur;a 6- to 12-membered polycyclic saturated or partially unsaturatedheterocycle having 1-5 heteroatoms independently selected from nitrogen,oxygen, or sulfur; and an 8- to 10-membered bicyclic heteroaryl ringhaving 1-5 heteroatoms independently selected from nitrogen, oxygen, orsulfur; wherein R⁵ and R⁶ can be taken together with intervening atomsto form one or more optionally substituted rings optionally containingone or more heteroatoms, and an R⁵ or R⁶ group can be taken with an R¹or R² group to form one or more optionally substituted rings; eachoccurrence of R⁸, R⁹, and R¹⁰ is independently hydrogen or an optionallysubstituted radical selected from the group consisting of C₁₋₂₀aliphatic; C₁₋₂₀ heteroaliphatic; phenyl; a 3- to 8-membered saturatedor partially unsaturated monocyclic carbocycle; a 7-14 carbon saturated,partially unsaturated or aromatic polycyclic carbocycle; a 5- to6-membered monocyclic heteroaryl ring having 1-4 heteroatomsindependently selected from nitrogen, oxygen, or sulfur; a 3- to8-membered saturated or partially unsaturated heterocyclic ring having1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur;a 6- to 12-membered polycyclic saturated or partially unsaturatedheterocycle having 1-5 heteroatoms independently selected from nitrogen,oxygen, or sulfur; and an 8- to 10-membered bicyclic heteroaryl ringhaving 1-5 heteroatoms independently selected from nitrogen, oxygen, orsulfur; wherein any two or more R⁸, R⁹ and R¹⁰ groups can be takentogether with intervening atoms to form one or more optionallysubstituted rings; each occurrence of R¹¹ is independently selected fromthe group consisting of: halogen, —NO₂, —CN, —SR^(y), —S(O)R^(y),—S(O)₂R^(y), —NR^(y)C(O)R, —OC(O)R^(y), —CO₂R, —NCO, —N₃, —OR⁷,—OC(O)N(R^(y))₂, —N(R)₂, —NR^(y)C(O)R^(y), —NR^(y)C(O)OR^(y); or anoptionally substituted radical selected from the group consisting ofC₁₋₂₀ aliphatic; C₁₋₂₀ heteroaliphatic; phenyl; a 3- to 8-memberedsaturated or partially unsaturated monocyclic carbocycle; a 7-14 carbonsaturated, partially unsaturated or aromatic polycyclic carbocycle; a 5-to 6-membered monocyclic heteroaryl ring having 1-4 heteroatomsindependently selected from nitrogen, oxygen, or sulfur; a 3- to8-membered saturated or partially unsaturated heterocyclic ring having1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur;a 6- to 12-membered polycyclic saturated or partially unsaturatedheterocycle having 1-5 heteroatoms independently selected from nitrogen,oxygen, or sulfur; and an 8- to 10-membered bicyclic heteroaryl ringhaving 1-5 heteroatoms independently selected from nitrogen, oxygen, orsulfur, where each occurrence of R^(y) is independently hydrogen or anoptionally substituted C₁₋₆ aliphatic group, and where two or moreadjacent R¹¹ groups can be taken together to form an optionallysubstituted saturated, partially unsaturated, or aromatic 5- to12-membered ring containing 0 to 4 heteroatoms; each occurrence of R⁷ isindependently hydrogen, a hydroxyl protecting group, or an optionallysubstituted radical selected from the group consisting of C₁₋₂₀ acyl;C₁₋₂₀ aliphatic; C₁₋₂₀ heteroaliphatic; phenyl; a 3- to 8-memberedsaturated or partially unsaturated monocyclic carbocycle; a 7-14 carbonsaturated, partially unsaturated or aromatic polycyclic carbocycle; a 5-to 6-membered monocyclic heteroaryl ring having 1-4 heteroatomsindependently selected from nitrogen, oxygen, or sulfur; a 3- to8-membered saturated or partially unsaturated heterocyclic ring having1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur;a 6- to 12-membered polycyclic saturated or partially unsaturatedheterocycle having 1-5 heteroatoms independently selected from nitrogen,oxygen, or sulfur; and an 8- to 10-membered bicyclic heteroaryl ringhaving 1-5 heteroatoms independently selected from nitrogen, oxygen, orsulfur; X⁻ is any anion; and Ring A is an optionally substituted, 5- to10-membered heteroaryl group.
 10. The metal complex according to claim2, wherein each linker moiety “

” is independently selected from an optionally substituted C₃-C₃₀aliphatic group.
 11. The metal complex according to claim 2, whereineach linker moiety “

” is independently selected from an optionally substituted C₄-C₆aliphatic group.
 12. The metal complex according to claim 2, whereineach linker moiety “

” is independently selected from optionally substituted C₄ aliphaticgroup.
 13. The metal complex according to claim 2, wherein each linkermoiety “

” is independently selected from optionally substituted C₃ aliphaticgroup.
 14. The metal complex according to claim 2, wherein each linkermoiety “

” is independently selected from the group consisting of:

wherein each occurrence of R^(y) is independently —H, or an optionallysubstituted radical selected from the group consisting of C₁₋₆aliphatic, 3- to 7-membered heterocyclic, phenyl, and 8- to 10-memberedaryl.
 15. The metal complex of claim 7, wherein one or more Z group(s)is independently selected from the group consisting of:

wherein each R¹ and R² is methyl; or


16. The metal complex of claim 8, wherein one or more Z group(s) isindependently selected from the group consisting of:


17. The metal complex of claim 9, wherein one or more Z group(s) isindependently selected from the group consisting of: